KR101575913B1 - Self-dispersed pigments and methods for making and using the same - Google Patents
Self-dispersed pigments and methods for making and using the same Download PDFInfo
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- C09B68/44—Non-ionic groups, e.g. halogen, OH or SH
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- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/46—Aromatic cyclic groups
- C09B68/467—Heteroaromatic groups
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- C09B68/46775—Triazine
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/56—Treatment of carbon black ; Purification
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09D11/00—Inks
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Abstract
X-[Y]n 반응성 기를 갖는 반응성 화합물을 이차 화합물 N-S-ZM과 반응시켜 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b를 형성하는 것을 포함하는 안료 개질 방법. 안료는 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b와 반응하여 안료의 표면에 치환된 반응성 중간체를 부착시켜 표면 개질된 안료를 형성한다. X는 설포닐, 포스포릴, 또는 1,3,5-트리아지닐 기일 수 있고, Y는 할로겐 이탈기일 수 있고, N은 염기성 친핵성 기일 수 있고, S는 유기 기일 수 있고, ZM은 이온화 말단기일 수 있다. 또한, n은 1 내지 3의 정수이고, b는 1 내지 3의 정수이고, a = n-b이다. n이 b와 같거나 그보다 더 크고 b가 2 또는 3인 경우, 각각의 N-S-ZM은 동일하거나 상이할 수 있다. Reacting a reactive compound having an X- [Y] n reactive group with a second compound NS-ZM to form a substituted reactive intermediate [Y] a -X- (NS-ZM) b . The pigment reacts with the substituted reactive intermediate [Y] a -X- (NS-ZM) b to attach the substituted reactive intermediate to the surface of the pigment to form a surface modified pigment. X may be a sulfonyl, phospholyl, or 1,3,5-triazinyl group, Y may be a halogen leaving group, N may be a basic nucleophilic group, S may be an organic group, and ZM is an ionizing end group . N is an integer of 1 to 3, b is an integer of 1 to 3, and a = nb. When n is equal to or greater than b and b is 2 or 3, each NS-ZM may be the same or different.
Description
관련 출원과의 상호-참조Inter-reference to related application - reference
본 출원은 35 U.S.C.§119(e) 하에서 2007년 8월 23일자로 출원된 미국 가특허 출원 제60/957,596호에 대한 우선권을 청구한다. 상기 출원의 전체 내용은 온전히 본원에 참고로 포함된다.This application claims priority to U.S. Provisional Patent Application No. 60 / 957,596, filed on August 23, 2007 under 35 USC § 119 (e). The entire contents of which are hereby incorporated by reference in their entirety.
사용 분야Field of use
본 발명은 자가-분산성 안료의 제조 방법에 관한 것이다. 보다 구체적으로, 본 발명은 안료의 표면 개질에 관한 것이다. 표면이 공유 결합을 통해 개질된 안료는 산업계에서 자가-분산성 안료로서 공지되어 있다. 표면 개질은 수성 환경에서 수행될 수 있고, 환경 친화적일 수 있다. 추가로, 본 발명은 코팅, 페인트, 종이, 접착제, 라텍스, 토너, 직물, 섬유, 플라스틱, 및 잉크를 비롯한 (이들로 한정되지는 않음), 표면-개질된 안료를 포함하는 최종 용도 적용에 관한 것이다. 최종 용도의 구체적인 예로는 종이, 직물, 섬유, 금속 데코 및 플라스틱용 인쇄 잉크, 우드 스테인, 필기 기구, 및 컬러 필터가 포함되나 이들로 한정되지는 않는다. 본 발명은 또한 잉크, 예컨대 잉크젯 잉크에 관한 것이다.The present invention relates to a process for the preparation of self-dispersible pigments. More specifically, the present invention relates to surface modification of pigments. Pigments whose surface has been modified via covalent bonding are known in the industry as self-dispersible pigments. Surface modification can be performed in an aqueous environment and can be environmentally friendly. In addition, the present invention relates to end-use applications involving surface-modified pigments, including but not limited to coatings, paints, paper, adhesives, latex, toners, fabrics, will be. Specific examples of end uses include, but are not limited to, printing inks for paper, textiles, fibers, metal decors and plastics, wood stains, writing instruments, and color filters. The present invention also relates to inks such as inkjet inks.
안료는 잉크, 코팅, 페인트, 종이, 접착제, 라텍스, 토너, 직물, 섬유, 우드 스테인, 컬러 필터, 및 플라스틱에 대해서, 수용성 염료에 비해 몇몇 장점을 제공한다. 안료는 수용성 염료보다 더 큰 광견뢰성(lightfastness), 수견뢰성(waterfastness), 광학 밀도 및 경계 명확성(edge acuity) 중 적어도 하나를 발휘할 수 있다. 불행히도, 안료는 또한 저장 동안 침강하는 성향이 더 크므로, 요구되는 적용, 예컨대 잉크젯 잉크에서의 그의 사용이 초기에 제한된다. 콜로이드 안정성을 위한 화학적 첨가제와 조합된, 안료 입자를 ㎛ 이하의 수준으로 분쇄하는 매체 밀(media mill)의 출현은 잉크젯 잉크 제제에서 안료 분산액의 사용을 추진시켰다. 그러나, 화학적 첨가제가 분산액의 점도를 증가시킬 수 있어, 잉크젯 프린트헤드의 작은 오리피스에서 잉크가 분사되기 어렵게 되었다. 게다가, 화학적 첨가제는 상기 나열된 물질의 제조에 현저한 비용을 부가시킬 수 있고, 따라서 경제적으로도 적합치 않다. 화학적 첨가제, 또는 분산제는 안료의 표면에 결합하지 않을 수 있으므로, 안정화는 불충분할 수 있다. 화학적 첨가제를 사용하는 현재의 염료-기반 시스템 및 안료 시스템과 전형적으로 연관된 적어도 일부의 문제를 해결하는, 특히 잉크젯 프린터에 사용하기 위한 개선된 잉크 조성물에 대한 필요성이 남아 있었다. 또한, 화학적 첨가제를 사용하는 현재의 염료-기반 시스템 및 안료 시스템과 전형적으로 연관된 적어도 일부의 문제를 해결하는 안료를 사용하는 개선된 물질에 대한 필요성이 남아 있었다.Pigments offer several advantages over water-soluble dyes for inks, coatings, paints, paper, adhesives, latex, toners, fabrics, fibers, wood stains, color filters, and plastics. The pigment can exhibit at least one of greater lightfastness, waterfastness, optical density and edge acuity than the water-soluble dye. Unfortunately, pigments are also more prone to sediment during storage, so their use in the required applications, such as inkjet inks, is initially limited. The advent of media mills, which, in combination with chemical additives for colloidal stability, pulverize pigment particles to sub-micron levels has propelled the use of pigment dispersions in ink jet ink formulations. However, chemical additives can increase the viscosity of the dispersion, making it difficult for ink to be ejected from small orifices of the inkjet printhead. In addition, chemical additives can add significant cost to the manufacture of the materials listed above, and are therefore not economically feasible. Chemical additives, or dispersants may not bond to the surface of the pigment, so stabilization may be insufficient. There remains a need for improved ink compositions for use in ink jet printers, particularly those that solve at least some of the problems typically associated with current dye-based systems and pigment systems using chemical additives. In addition, there remains a need for improved materials using pigments that solve at least some of the problems typically associated with current dye-based systems and pigment systems that use chemical additives.
요약summary
한 측면에서, 본 발명은 시아누릭 클로라이드를 약 3 당량의 이차 화합물 또는 이차 화합물의 혼합물과 반응시켜 모든 반응성 염소를 치환시켜 치환된 트리아진을 형성하는 것을 포함할 수 있는 안료 개질 방법을 제공할 수 있다. 치환된 트리아진은 안료의 표면과 반응하여 표면 개질된 안료를 형성할 수 있다. In one aspect, the present invention can provide a pigment modification method that can include reacting cyanuric chloride with about 3 equivalents of a secondary compound or a mixture of secondary compounds to displace all reactive chlorine to form the substituted triazine have. Substituted triazines can react with the surface of the pigment to form a surface modified pigment.
또다른 측면에서, 본 발명은 X-[Y]n 반응성 기를 갖는 반응성 화합물을 이차 화합물 N-S-ZM과 반응시켜 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b를 형성하는 단계를 포함할 수 있는 안료 개질 방법을 제공할 수 있다. 상기 방법은 또한 안료를 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b와 반응시켜 치환된 반응성 중간체를 안료의 표면에 부착시킴으로써 표면 개질된 안료를 형성하는 단계를 포함할 수 있다. X는 설포닐, 포스포릴, 또는 1,3,5-트리아지닐 기일 수 있다. Y는 할로겐 이탈기일 수 있고, N은 친핵성 기일 수 있고, S는 유기 기일 수 있고, ZM은 이온화 말단기일 수 있다. 또한, n은 1 내지 3의 정수일 수 있고, b는 1 내지 3의 정수일 수 있고, a = n-b이다. n이 b와 같거나 더 큰 경우, 그리고 b가 2 또는 3인 경우, 각각의 N-S-ZM은 동일하거나 상이할 수 있다. In another aspect, the present invention provides a process for preparing a substituted reactive intermediate [Y] a -X- (NS-ZM) b by reacting a reactive compound having an X- [Y] n reactive group with a secondary compound NS- To provide a pigment modification method which can be incorporated. The method may also include forming a surface modified pigment by reacting the pigment with the substituted reactive intermediate [Y] a -X- (NS-ZM) b to attach the substituted reactive intermediate to the surface of the pigment . X may be a sulfonyl, phosphoryl, or 1,3,5-triazinyl group. Y may be a halogen leaving group, N may be a nucleophilic group, S may be an organic group, and ZM may be an ionizing end group. N may be an integer of 1 to 3, b may be an integer of 1 to 3, and a = nb. When n is equal to or greater than b and b is 2 or 3, each NS-ZM may be the same or different.
또다른 측면에서, 본 발명은 반응성 기를 안료의 표면에 부착시키는 단계를 포함할 수 있는 안료 개질 방법을 제공할 수 있다. 그 후, 반응성 기를 이온화 말단기를 가진 유기 기질로 치환시킬 수 있다. 안료는 적색 안료 122, 보라색 안료 19, 보라색 안료 23, 적색 안료 202, 적색 안료 188, 황색 안료 155, 황색 안료 97, 녹색 안료 7, 청색 안료 15:3, 청색 안료 15:4, 및 황색 안료 74로 이루어진 군으로부터 선택될 수 있다. In another aspect, the present invention can provide a pigment modification method, which may include attaching a reactive group to the surface of the pigment. The reactive group can then be replaced with an organic substrate having an ionizing end group. The pigments include
추가의 측면에서, 본 발명은 반응성 기 X-Y를 안료의 표면에 부착시키는 단계를 포함할 수 있는 안료 개질 방법을 제공할 수 있다. 그 후, Y를 유기 기질 N-S-ZM으로 치환시켜 X-N-S-ZM이 부착된 표면-개질된 안료를 형성할 수 있다. X는 설포닐, 포스포릴, 또는 1,3,5-트리아진 기일 수 있다. Y는 불소, 염소, 브롬, 또는 요오드일 수 있다. N은 아민, 이민, 피리딘, 또는 티올 기일 수 있다. S는 분자량이 약 300 내지 약 8000 범위인 치환 또는 비치환된 알킬, 아릴 또는 중합체 쇄일 수 있다. Z는 카르복실, 설포닐, 페놀릭, 포스포릴, 암모늄, 트리메틸암모늄, 또는 트리부틸암모늄 기일 수 있다. M은 할라이드, 음으로 하전된 이온, 염 형태인 양성자, 또는 염 형태인 양이온일 수 있다. In a further aspect, the present invention may provide a pigment modification method which may include attaching the reactive group X-Y to the surface of the pigment. Subsequently, Y can be replaced with an organic substrate N-S-ZM to form a surface-modified pigment with X-N-S-ZM attached thereto. X may be a sulfonyl, phosphoryl, or 1,3,5-triazine group. Y may be fluorine, chlorine, bromine, or iodine. N may be an amine, an imine, a pyridine, or a thiol group. S may be a substituted or unsubstituted alkyl, aryl, or polymer chain having a molecular weight in the range of from about 300 to about 8000. Z may be a carboxyl, sulfonyl, phenolic, phospholyl, ammonium, trimethylammonium, or tributylammonium group. M can be a halide, a negatively charged ion, a salt in the form of a proton, or a salt in the form of a cation.
본 발명의 다른 측면은 상세한 설명 및 첨부 도면을 고려할 때 명백할 것이다.Other aspects of the invention will be apparent upon consideration of the detailed description and the accompanying drawings.
도 1은 미처리된 카본 블랙 샘플 및 실시예 1, 20, 31, 및 41로부터의 카본 블랙 샘플에 대한 저해상도 X-선 광전자 분광법 (XPS) 스펙트럼을 나타낸다.
도 2는 미처리된 카본 블랙 샘플 및 실시예 1, 20, 31, 및 41로부터의 카본 블랙 샘플에 대한 고해상도 N1s XPS 스펙트럼을 나타낸다.
도 3은 미처리된 카본 블랙 샘플 및 실시예 1, 20, 31, 및 41로부터의 카본 블랙 샘플에 대한 고해상도 O1s XPS 스펙트럼을 나타낸다.
도 4는 미처리된 카본 블랙 샘플 및 실시예 1, 20, 31, 및 41로부터의 카본 블랙 샘플에 대한 고해상도 S2p XPS 스펙트럼을 나타낸다.
도 5는 미처리된 청색 안료 15 샘플 및 실시예 7, 9, 11, 16, 및 42로부터의 청색 안료 15 샘플에 대한 저해상도 XPS 스펙트럼을 나타낸다.
도 6은 미처리된 청색 안료 15 샘플 및 실시예 7, 9, 11, 16, 및 42로부터의 청색 안료 15 샘플에 대한 고해상도 O1s XPS 스펙트럼을 나타낸다.
도 7은 미처리된 청색 안료 15 샘플 및 실시예 7, 9, 11, 16, 및 42로부터의 청색 안료 15 샘플에 대한 고해상도 Na1s XPS 스펙트럼을 나타낸다.
도 8은 미처리된 적색 안료 122번 샘플 및 실시예 14, 21, 37, 및 45로부터의 적색 안료 122번 샘플에 대한 저해상도 XPS 스펙트럼을 나타낸다.
도 9는 미처리된 적색 안료 122번 샘플 및 실시예 14, 21, 37, 및 45로부터의 적색 안료 122번 샘플에 대한 고해상도 O1s XPS 스펙트럼을 나타낸다.
도 10은 실시예 14, 21, 37, 및 45로부터의 적색 안료 122번 샘플에 대한 고해상도 Na1s XPS 스펙트럼을 나타낸다.
도 11은 실시예 14, 21, 37, 및 45로부터의 적색 안료 122번 샘플에 대한 고해상도 S2p XPS 스펙트럼을 나타낸다.
도 12는 미처리된 황색 안료 74번 샘플 및 실시예 15, 29, 및 46으로부터의 황색 안료 74번 샘플에 대한 저해상도 XPS 스펙트럼을 나타낸다.
도 13은 미처리된 황색 안료 74번 샘플 및 실시예 15, 29, 및 46으로부터의 황색 안료 74번 샘플에 대한 고해상도 C1s XPS 스펙트럼을 나타낸다.
도 14는 미처리된 황색 안료 74번 샘플 및 실시예 15, 29, 및 46으로부터의 황색 안료 74번 샘플에 대한 고해상도 O1s XPS 스펙트럼을 나타낸다. 1 shows a low resolution X-ray photoelectron spectroscopy (XPS) spectrum of untreated carbon black samples and carbon black samples from Examples 1, 20, 31,
Figure 2 shows the high resolution N1s XPS spectra for untreated carbon black samples and carbon black samples from Examples 1, 20, 31 and 41.
Figure 3 shows a high resolution O1s XPS spectrum for untreated carbon black samples and carbon black samples from Examples 1, 20, 31, and 41.
Figure 4 shows a high resolution S2p XPS spectrum for untreated carbon black samples and carbon black samples from Examples 1, 20, 31 and 41.
Figure 5 shows the low-resolution XPS spectra for the untreated
Figure 6 shows a high resolution O1s XPS spectrum for a sample of untreated
Figure 7 shows the high resolution Na1s XPS spectra for the untreated
Figure 8 shows a low-resolution XPS spectrum for the
Figure 9 shows the high resolution O1s XPS spectrum for the red pigment sample No. 122 from the untreated red pigment sample and the red pigment sample from Examples 14, 21, 37, and 45. FIG.
10 shows high resolution Na1s XPS spectra for
11 shows a high resolution S2p XPS spectrum for
Figure 12 shows a low-resolution XPS spectrum for the
Figure 13 shows a high resolution C1s XPS spectrum for the
Figure 14 shows the high resolution O1s XPS spectrum for the
본 발명의 임의의 실시양태를 상세하게 설명하기 전에, 본 발명은 하기 설명에 기재된 구조의 세부사항 및 성분의 배열에 본 발명을 적용시키는 것으로 한정되지 않음을 이해해야 한다. 본 발명은 다른 실시양태가 가능하고, 다양한 방법으로 실시되거나 수행될 수 있다. 또한, 본원에 사용된 어구 및 용어는 설명의 목적이며, 한정되는 것으로 인식해서는 안됨을 이해해야 한다. 본원에서 "비롯한", "포함하는", 또는 "갖는" 및 그의 변형은 그 앞에 나열된 항목 및 그의 등가물 뿐만 아니라 추가의 항목을 포함하는 것을 의미한다.Before describing in detail certain embodiments of the invention, it is to be understood that the invention is not limited to applying the invention to the details of construction and arrangement of components set forth in the following description. The invention is capable of other embodiments and of being practiced or carried out in various ways. It is also to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting. As used herein, the terms "comprising", "comprising", or "having" and variations thereof mean inclusion of the items listed thereon and equivalents thereof as well as additional items.
또한, 본원에 언급된 임의의 수치 범위는 낮은 값에서부터 높은 값까지의 모든 값을 포함하는 것으로 이해한다. 예를 들면, 농도 범위가 1% 내지 50%라고 기재된 경우, 예컨대 2% 내지 40%, 10% 내지 30%, 또는 1% 내지 3% 등의 값이 본 명세서에 명백히 열거된 것으로 의도된다. 이는 무엇이 구체적으로 의도되는 지에 대한 예일 뿐이며, 열거된 최저 값과 최고 값을 포함하여 그 사이에 있는 모든 가능한 수치의 조합이 본원에서 명백히 기재된 것으로 간주해야 한다.It is also understood that any numerical range mentioned herein includes all values from a low value to a high value. For example, where a concentration range is described as 1% to 50%, values such as 2% to 40%, 10% to 30%, or 1% to 3% are intended to be expressly recited herein. It is to be understood that this is merely an example of what is specifically intended, and the combination of all possible values in between, including the recited lowest and highest values, shall be regarded as being expressly set forth herein.
한 실시양태에서, 본 발명은 안료 개질 방법을 제공한다. 상기 방법은 반응성 분자의 중개를 통하여 유기 기를 하전된 말단기 (음 또는 양)와 부착시켜 표면 안정화된 개질된 안료를 생성하는 것을 포함할 수 있다. 이론에 제한되지 않으면서, 안정화는 척력에 의한 ㎛ 이하 크기의 안료 입자에 공유 부착된 유사하게 하전된 기의 동등한 분포에 의해 달성된다고 여겨진다. In one embodiment, the present invention provides a pigment modification method. The method may include attaching the organic group to the charged terminal group (negative or positive) through intermediation of the reactive molecule to produce a surface stabilized modified pigment. Without being limited by theory, it is believed that stabilization is achieved by an equivalent distribution of similarly charged groups covalently attached to pigment particles of sub-micron size by repulsion.
또다른 실시양태에서, 본 발명은 안료 개질 방법을 제공한다. 상기 방법은 나중에 상기 기재된 바와 같은 적합한 유기 분자와 반응하는 반응성 설포닐 클로라이드 중간체를 형성하기 위한 클로로설폰화 단계를 포함할 수 있다. 한 측면에서, 클로로설폰화의 정도를 증가시켜 액체 겔 또는 미셸-유사 조성물을 수득할 수 있고, 이는 미처리된 안료와 밀링시 안정한 분산액을 형성한다.In another embodiment, the present invention provides a pigment modification method. The method may comprise a chlorosulfonation step to form a reactive sulfonyl chloride intermediate which is then reacted with a suitable organic molecule as described above. In one aspect, the degree of chlorosulfonation may be increased to obtain a liquid gel or micelle-like composition, which forms a stable dispersion upon milling with the untreated pigment.
또다른 실시양태에서, 본 발명은 상기 기재된 바와 같은 적합한 유기 분자에 부착된 반응성 중간체와 안료의 반응에 의해 형성된 자가-분산성 안료를 포함하는 분산액을 제공한다. 수성 환경에서 안정한 반응성 중간체의 선택은 본 발명의 또다른 측면이다. In another embodiment, the invention provides a dispersion comprising a self-dispersible pigment formed by the reaction of a pigment with a reactive intermediate attached to a suitable organic molecule as described above. The selection of stable reactive intermediates in an aqueous environment is another aspect of the present invention.
또다른 실시양태에서, 본 발명은 안료의 표면에 반응성 기를 부착시키고, 그 후, 상기 반응성 기를 이온화 말단기를 가진 유기 기질로 치환시키는 것을 포함할 수 있는 안료 개질 방법을 제공한다. In another embodiment, the present invention provides a pigment modification method which can include attaching a reactive group to the surface of the pigment, and then replacing the reactive group with an organic substrate having an ionizing end group.
추가의 실시양태에서, 본 발명은 안료 1 g 당 약 0.01 내지 약 1.0 mMole의 S 및 약 0.01 내지 약 2.0 mMole의 활성 수소, 및 물을 포함하는 자가-분산성 안료를 포함하는 분산액을 제공한다. 또다른 실시양태에서, 본 발명은 안료 1 g 당 약 0.06 내지 약 0.7 mMole의 S 및 약 0.07 내지 약 1.6 mMole의 활성 수소, 및 물을 포함하는 자가-분산성 안료를 포함하는 분산액을 제공한다. In a further embodiment, the present invention provides a dispersion comprising from about 0.01 to about 1.0 mMole of S per g of pigment and from about 0.01 to about 2.0 mMole of active hydrogen, and a water-containing self-dispersible pigment. In another embodiment, the present invention provides a dispersion comprising from about 0.06 to about 0.7 mMole of S and from about 0.07 to about 1.6 mMole of active hydrogen per gram of pigment, and a water-containing self-dispersible pigment.
자가-분산성 안료의 제조 방법Manufacturing method of self-dispersible pigment
본 발명의 한 측면은 안정한 자가-분산성 안료의 제조 방법에 관한 것이다.One aspect of the invention relates to a process for the preparation of stable self-dispersible pigments.
본원에 사용되는 용어 "안료"는 기재, 예컨대 일반 용지 또는 코팅지, 필름 및 다른 유형의 수용 매체에 색상을 부여하기 위해 사용되는, 용매 매질 중에서 불용성인 것을 의미한다. 안료는 흑색일 수 있을 뿐만 아니라 다른 색상일 수도 있다.As used herein, the term "pigment" means insoluble in a solvent medium, which is used to impart color to a substrate, such as plain paper or coated paper, film and other types of receiving media. The pigment may be black as well as other colors.
본원에 사용되는 용어 "자가-분산성" 안료는 그의 표면에 공유적으로 부착된 안정한 기를 갖는 안료를 의미하며, 안료가 임의의 추가 분산화제 없이도 안정한 수분산액을 형성하도록 한다.The term "self-dispersible" pigment as used herein refers to a pigment having a stable group covalently attached to its surface, such that the pigment forms a stable aqueous dispersion without any additional dispersants.
본원에 사용되는 용어 "안정한"은, 분산액이 주위 온도에서 적어도 약 3개월 내지 6개월 내지 2년의 기간에 걸쳐 저장되는 경우에, 시간의 흐름에 따라 상기 분산액이 주요 특성 (예컨대 평균 입도, 점도, 표면 장력 및 pH 중 적어도 하나)의 측정시에 10% 미만으로 변화하는 것으로 증명되는 바와 같은 최소의 변화를 경험하게 되는 것을 의미한다. 가속화된 시험 방법으로는 약 1주 이상 동안 약 70℃에서의 열 안정성 시험 또는 약 4주 이상 동안 약 70℃에서의 열 안정성 시험이 포함된다.As used herein, the term "stable" means that, when the dispersion is stored over a period of at least about 3 months to 6 months to 2 years at ambient temperature, the dispersion has a major property , At least one of surface tension, and pH), as measured by a change in the thickness of the substrate. Accelerated testing methods include thermal stability testing at about 70 ° C for about one week or more, or thermal stability testing at about 70 ° C for about four weeks or more.
제1 실시양태에서, 자가-분산성 안료의 제조 방법은 일반적으로 (1) 안료 (P)를 X-Y 반응성 기를 갖는 반응성 화합물 및 할로겐-함유 시약과 반응시켜 반응성 기 X-Y를 안료 (P)의 표면에 부착시키고, 이에 따라 안료 반응성 중간체 (P)X-Y를 형성하는 단계; 및 (2) 안료 반응성 중간체 (P)X-Y를 이차 화합물 N-S-ZM과 반응시켜 자가-분산성 안료 (P)-X-S-ZM을 형성하는 단계 ("치환 단계")를 포함한다. 이 실시양태의 한 예로는, 이들로 한정되지는 않지만, 반응성 기 X-Y를 안료의 표면에 부착시키는 단계; 및 그 후, Y를 유기 기질 N-S-ZM으로 치환하여 X-N-S-ZM이 부착된 표면 개질된 안료를 형성하는 단계를 포함할 수 있는 안료 개질 방법이 포함될 수 있다. (1) reacting the pigment (P) with a reactive compound having an XY reactive group and a halogen-containing reagent to form a reactive group XY on the surface of the pigment (P) To form a pigment reactive intermediate (P) XY; And (2) reacting the pigment reactive intermediate (P) X-Y with a secondary compound N-S-ZM to form a self-dispersible pigment (P) -X-S-ZM ("displacement step"). One example of this embodiment includes, but is not limited to, attaching the reactive group X-Y to the surface of the pigment; And thereafter, replacing Y with an organic substrate N-S-ZM to form a surface modified pigment having X-N-S-ZM attached thereto.
제2 실시양태에서, 자가-분산성 안료 (P)-X-S-ZM의 제조 방법은 (1) X-Y 반응성 기를 갖는 반응성 화합물을 이차 화합물 N-S-ZM과 반응시켜 치환된 반응성 중간체 X-S-ZM을 형성하는 단계 ("치환 단계"); 및 (2) 안료 (P)를 치환된 반응성 중간체 X-S-ZM과 반응시켜 치환된 반응성 중간체 X-S-ZM을 2급 치환 반응을 이용하여 안료의 표면에 부착시킴으로써 자가-분산성 안료 (P)-X-S-ZM을 형성하는 단계를 포함할 수 있다. 이 실시양태의 한 예로는, 이들로 한정되지는 않지만, X-[Y]n 반응성 기를 갖는 반응성 화합물을 이차 화합물 N-S-ZM과 반응시켜 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b를 형성하는 단계; 및 안료를 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b와 반응시켜 치환된 반응성 중간체를 안료의 표면에 부착시킴으로써 표면 개질된 안료를 형성하는 단계를 포함할 수 있는 안료 개질 방법 (여기서, n은 1 내지 3의 정수이고; b는 1 내지 3의 정수이고; a=n-b이고; 이때 n은 b와 같거나 그보다 더 크고, b가 2 또는 3인 경우, 각각의 N-S-ZM은 동일하거나 상이할 수 있음)이 포함된다. 한 실시양태에서, b가 2 또는 3인 경우, 각각의 N-S-ZM은 상이할 수 있다.In a second embodiment, a process for preparing a self-dispersible pigment (P) -XS-ZM comprises the steps of (1) reacting a reactive compound having an XY reactive group with a second compound NS-ZM to form a substituted reactive intermediate XS-ZM Step ("substitution step"); And (2) reacting the pigment (P) with the substituted reactive intermediate XS-ZM to attach the substituted reactive intermediate XS-ZM to the surface of the pigment using a secondary substitution reaction to form a self-dispersing pigment (P) -XS -ZM. ≪ / RTI > One example of this embodiment includes, but is not limited to, reacting a reactive compound having an X- [Y] n reactive group with a secondary compound NS-ZM to form a substituted reactive intermediate [Y] a -X- b ) < / RTI > And reacting the pigment with a substituted reactive intermediate [Y] a -X- (NS-ZM) b to attach the substituted reactive intermediate to the surface of the pigment to form a surface modified pigment Where n is an integer from 1 to 3, b is an integer from 1 to 3, a = nb, where n is equal to or greater than b and b is 2 or 3, each NS-ZM May be the same or different. In one embodiment, when b is 2 or 3, each NS-ZM may be different.
제3 실시양태에서, 자가-분산성 안료 (P)-X-S-ZM의 제조 방법은 (1) X-Y 반응성 기를 갖는 반응성 화합물을 이차 화합물 N-S-ZM과 반응시켜 치환된 제1 반응성 중간체 X-S-ZM을 형성하는 단계 ("치환 단계"); (2) X-Y 반응성 기를 갖는 반응성 화합물을 단계 (1)과 상이한 이차 화합물 N2-S2-Z2M2과 반응시켜 치환된 제2 반응성 중간체 X-S2-Z2M2를 형성하는 단계 ("치환 단계"); (3) 안료 (P)를 치환된 반응성 중간체 X-S-ZM 및 X-S2-Z2M2와 반응시켜 치환된 반응성 중간체에 부착시킴으로써 자가-분산성 안료 Z2M2-S2-X-(P)-X-S-ZM를 형성하는 단계를 포함할 수 있다. 임의로 S-ZM 및 S2-Z2M2는 동일할 수 있으며, 모든 반응성 기는 치환될 것이다. 안료 표면으로의 최종 부착은 라디칼 보조의 불균등화(disproportionation) 반응 중 하나일 수 있다. In a third embodiment, the process for preparing a self-dispersible pigment (P) -XS-ZM comprises the steps of (1) reacting a reactive compound having an XY reactive group with a second compound NS-ZM to form a substituted first reactive intermediate XS- ("Substitution step"); (2) reacting a reactive compound having an X-Y reactive group with a second compound different from step (1) N2-S2-Z2M2 to form a substituted second reactive intermediate X-S2-Z2M2 ("substitution step"); (3) The self-dispersing pigment Z2M2-S2-X- (P) -XS-ZM is prepared by reacting the pigment (P) with the substituted reactive intermediates XS-ZM and X- To form a second layer. Optionally S-ZM and S2-Z2M2 may be the same and all reactive groups will be substituted. The final attachment to the pigment surface can be one of the radical-assisted disproportionation reactions.
제4 실시양태에서, 자가-분산성 안료 (P)-X-S-ZM의 제조 방법은 (1) 분쇄 보조제를 사용하고, 안료를 밀링하고 분산시켜 안료 수분산액을 형성하는 단계; (2) X-Y 반응성 기를 갖는 반응성 화합물을 이차 화합물 N-S-ZM과 반응시켜 치환된 제1 반응성 중간체 X-S-ZM을 형성하는 단계 ("치환 단계"); (3) X-Y 반응성 기를 갖는 반응성 화합물 단계 (2)와 상이한 이차 화합물 N2-S2-Z2M2와 반응시켜 치환된 제2 반응성 중간체 X-S2-Z2M2를 형성하는 단계 ("치환 단계"); (4) 분쇄 보조제와 함께 미리-밀링된 안료 (P)를 치환된 반응성 중간체 X-S-ZM 및 X-S2-Z2M2와 반응시켜 치환된 반응성 중간체 X-S-ZM 및 X-S2-Z2M2를 라디칼 개시 반응을 이용하여 안료의 표면에 부착시킴으로써 자가-분산성 안료 Z2M2-S2-X-(P)(R)-X-S-ZM을 형성하는 단계; 및 (5) 자가-분산성 안료를 정제하여 분쇄 보조제를 비롯한 불순물을 제거하는 단계를 포함할 수 있다. 임의로 S-ZM 및 S2-Z2M2는 동일한 것일 수 있다.In a fourth embodiment, the process for preparing the self-dispersible pigment (P) -X-S-ZM comprises the steps of: (1) milling and dispersing the pigment using a grinding aid to form a pigment water dispersion; (2) reacting a reactive compound having an X-Y reactive group with a second compound N-S-ZM to form a substituted first reactive intermediate X-S-ZM ("substitution step"); (3) Reactive compound having an X-Y reactive group (step "Substitution step") to form a substituted second reactive intermediate X-S2-Z2M2 by reacting with a second compound N2-S2-Z2M2 different from step (2); (4) reacting the substituted reactive intermediates XS-ZM and X-S2-Z2M2 with the pre-milled pigment (P) with the substituted reactive intermediates XS-ZM and X-S2- To form a self-dispersing pigment Z2M2-S2-X- (P) (R) -XS-ZM by attaching it to the surface of the pigment; And (5) purifying the self-dispersing pigment to remove impurities including grinding aids. Optionally, S-ZM and S2-Z2M2 may be the same.
이들 각각의 실시양태에서, 반응성 화합물은 X-Y 반응성 기를 가질 수 있으며, 여기서 X는, 이들로 한정되지는 않지만, 카르보닐, 설포닐, 포스포릴, 시아누릴 및 NH를 포함할 수 있고, Y는, 이들로 한정되지는 않지만, 플루오라이드, 클로라이드, 브로마이드 및 요오다이드를 포함하나 이들로 한정되지는 않는 산 할라이드 이탈기를 포함할 수 있다. 적합한 한 실시양태에서, X는 설포닐, 포스포릴 또는 시아누릴 (1,3,5-트리아지닐)일 수 있다. 산 할라이드 형성 시약은 할로겐을 함유한다. 이러한 시약의 예로는, 이들로 한정되지는 않지만, 클로로설폰산, 티오닐 클로라이드, 포스포릴 클로라이드, 및 이들의 조합이 포함된다. 이들 화합물에서 염소를 다른 할로겐으로 치환할 수 있다. 반응성 화합물은 짧은 지속기간 동안 저온에서 수성 매질 중에서 안정할 수 있다. In each of these embodiments, the reactive compound may have an XY reactive group, wherein X may include, but is not limited to, carbonyl, sulfonyl, phosphoryl, cyanuryl, and NH, But are not limited to, acid halide leaving groups including, but not limited to, fluorides, chlorides, bromides, and iodides. In a suitable embodiment, X may be a sulfonyl, phosphoryl or cyanuryl (1,3,5-triazinyl). The acid halide forming reagent contains a halogen. Examples of such reagents include, but are not limited to, chlorosulfonic acid, thionyl chloride, phosphoryl chloride, and combinations thereof. In these compounds, chlorine can be replaced by another halogen. The reactive compound may be stable in the aqueous medium at low temperatures for short durations.
치환 단계 동안, X-Y 반응성 기 중 하나 이상의 이탈기 Y는 이차 화합물 N-S-ZM으로 치환되며, 여기서 N은 친핵성 기, 예컨대 아민, 이민, 피리딘 또는 티올이고, S는, 이들로 한정되지는 않지만, 유기 기, 예컨대 약 1 내지 100개 초과의 탄소를 갖거나 또는 분자량이 약 300 내지 약 8000 범위인 치환 또는 비치환된 알킬, 아릴 및 중합체 쇄를 포함할 수 있고, 음 전하에 의한 안정화의 경우에, ZM은 산성 꼬리(tail) 기이고, 여기서 Z는, 이들로 한정되지는 않지만, 카르복실, 설포닐, 페놀릭 및 포스포릴일 수 있고, M은 이것이 염 형태로 존재하는 경우 양성자 또는 양이온일 수 있다. 이러한 치환은 안료의 표면에 전하 및 용적을 부여할 수 있다. 치환 단계는 수성 매질 중에서 수행될 수 있다. 산성 꼬리에서의 관능기의 선택은 최종 적용에 따라 지정되지만, 염기성 헤드에서의 관능기는 이탈기 Y를 치환시키기에 충분한 친핵성을 가져야만 한다. 이차 화합물로는 중합체, 아민, 아미노산, 알코올, 티올 및 이들의 조합이 포함될 수 있다. 이차 화합물 및 N2-S2-Z2M2 N-S-ZM의 예로는, 이들로 한정되지는 않지만, 아미노 벤조산, 아미노 벤젠 설폰산, 아미노 페놀, 아미노 설폰산, 폴리에톡실화 아미노산, 나트륨 설파닐레이트, 설파닐산, 나트륨 p-아미노벤조에이트, p-아미노페놀, 에틸 4-아미노벤조에이트, 타우린, 올레산 (아미노), 나트륨 아미노올레에이트, 테트라메틸암모늄 4-아미노벤조에이트 및 나트륨 4-아미노페놀레이트가 포함된다. 추가의 이차 화합물로는 유기 중합체 기질이 포함된다. 유기 중합체 기질의 예로는, 이들로 한정되지는 않지만, 공지된 분자량 범위가 300-3000 MW인 선형 알킬 및 분지형 에톡시 및 프로폭시 쇄 중합체 (헌츠만 케미칼스(Huntsman Chemicals)로부터 상표명 "설폰아민스(Surfonamines)"로 구입가능함), 선형 폴리에톡시 중합체 아민, 선형 프로폭시 중합체 아민, 스티렌 아크릴계 공중합체 (존슨 폴리머스(Johnson Polymers)로부터 상표명 "존크릴스(Joncryls)"로 구입가능함) 및 폴리에틸렌이민 (상표명 "에포민스(Epomines)"로 판매됨)이 포함될 수 있다. During the substitution step, at least one leaving group Y of the XY reactive group is replaced by a secondary compound NS-ZM, wherein N is a nucleophilic group such as an amine, an imine, a pyridine or a thiol, and S is, Aryl, and polymeric chains having an organic group, such as from about 1 to more than 100 carbons, or a molecular weight ranging from about 300 to about 8000, and in the case of stabilization by negative charge , ZM is an acidic tail group, where Z may be, but is not limited to, carboxyl, sulfonyl, phenolic and phosphoryl, and M is a proton or cationic . Such substitution can impart charge and volume to the surface of the pigment. The displacement step can be carried out in an aqueous medium. The selection of the functional group in the acidic tail is specified according to the final application, but the functional group in the basic head must have nucleophilicity sufficient to displace the leaving group Y. [ The secondary compounds may include polymers, amines, amino acids, alcohols, thiols, and combinations thereof. Examples of secondary compounds and N2-S2-Z2M2 NS-ZM include, but are not limited to, aminobenzoic acid, aminobenzenesulfonic acid, aminophenol, aminosulfonic acid, polyethoxylated amino acid, sodium sulfanilate, , Sodium p-aminobenzoate, p-aminophenol, ethyl 4-aminobenzoate, taurine, oleic acid (amino), sodium aminooleate, tetramethylammonium 4-aminobenzoate and sodium 4-aminophenolate . Additional secondary compounds include organic polymeric substrates. Examples of organic polymeric substrates include, but are not limited to, linear alkyl and branched ethoxy and propoxy chain polymers having a known molecular weight range of 300-3000 MW (available from Huntsman Chemicals under the trade name "Sulfonamines "Quot; Surfonamines "), linear polyethoxy polymer amines, linear propoxy polymer amines, styrene acrylic copolymers (available under the trade designation" Joncryls " from Johnson Polymers) Polyethyleneimine (sold under the trademark "Epomines").
양전하에 의한 안정화의 경우에, ZM은 양으로 하전된 4급 암모늄 유형의 꼬리 기일 수 있으며, 여기서 Z는, 이들로 한정되지는 않지만, 암모늄, 트리메틸암모늄 및 트리부틸암모늄일 수 있고, M은 할라이드 또는 음으로 하전된 임의의 이온일 수 있다. 이차 화합물 N-S-ZM 및 N2-S2-Z2M2의 예로는, 이들로 한정되지는 않지만, 폴리에틸렌이민, 폴리구아니딘, 4급 암모늄 화합물 등으로 이루어진 단순한 디아미노 방향족 또는 양이온성 중합체가 포함된다.In the case of stabilization by positive charge, ZM may be a positively charged quaternary ammonium type tail, where Z may be, but is not limited to, ammonium, trimethylammonium and tributylammonium, and M is halide Or any negatively charged ions. Examples of the secondary compounds N-S-ZM and N2-S2-Z2M2 include, but are not limited to, simple diamino aromatic or cationic polymers composed of polyethyleneimine, polyguanidine, quaternary ammonium compounds and the like.
최종 자가-분산성 안료는 제1 및 제2 실시양태에 대하여 화학식 (P)-X-S-ZM으로 나타낼 수 있다. 일부 예에서, 상이한 이차 화합물을 포함하는 안료에 부착된 다중 -S-ZM이 존재할 수 있다. 제3 실시양태에 대하여, 최종 자가-분산성 안료는 화학식 Z2M2-S2-X-(P)-X-S-ZM으로 나타낼 수 있다. 최종적으로, N, Z, M 및 S를 변형하기 위해 "2"를 사용하는 것은 N2, Z2, M2 및 S2가 N, Z, M 및 S와 동일하거나 상이할 수 있음을 표시하는 것을 의미한다. N2, Z2, M2 및 S2는 N, Z, M 및 S에 대하여 상기 기재된 동일한 선택사항으로부터 선택될 수 있다.The final self-dispersible pigment can be represented by the formula (P) -X-S-ZM for the first and second embodiments. In some instances, there may be multiple-S-ZM attached to a pigment comprising different secondary compounds. For the third embodiment, the resulting self-dispersible pigment may be represented by the formula Z2M2-S2-X- (P) -X-S-ZM. Finally, using "2 " to modify N, Z, M and S means to indicate that N2, Z2, M2 and S2 may be the same or different from N, Z, M and S. N2, Z2, M2 and S2 may be selected from the same options described above for N, Z, M and S.
본 발명을 설명하기 위해, 제1 실시양태의 특정 예는 하기에 제공되며, 여기서 P는 안료를 나타낸다. To illustrate the present invention, specific examples of the first embodiment are provided below, wherein P represents a pigment.
본 발명을 설명하기 위해, 제2 실시양태의 특정 예는 하기에 제공되며, 여기서 P는 안료를 나타낸다. To illustrate the present invention, specific examples of the second embodiment are provided below, wherein P represents a pigment.
본 발명을 설명하기 위해, 제3 실시양태의 특정 예는 하기에 제공되며, 여기서 P는 안료를 나타낸다. To illustrate the invention, specific examples of the third embodiment are provided below, wherein P represents a pigment.
본 발명의 실시양태는 하기에 보다 상세하게 논의된다. 일반적으로, 자가-분산성 안료의 제조 방법은 안료 공급원을 선택하는 것에서 출발한다. Embodiments of the present invention are discussed in more detail below. Generally, the process for the preparation of the self-dispersing pigment starts with the selection of the pigment source.
안료Pigment
본 발명에 따라 표면 개질될 수 있는 안료로는 이들로 한정되지는 않지만 아조 안료, 프탈로시아닌 안료, 안트라퀴논 안료, 퀴나크리돈 안료, 티오인디고 안료, 트리페닐메탄 레이크 안료 및 옥사진 레이크 안료가 포함된다. 구체적으로, 황색을 갖는 안료로는, 예를 들면, 씨. 아이. 황색 안료 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 16, 17, 65, 74, 83, 97, 138, 150, 151 및 155가 포함된다. 적색을 갖는 안료로는, 예를 들면, 씨. 아이. 적색 안료 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 41, 48, 49, 50, 51, 52, 57, 58, 60, 64, 83, 88, 89, 90, 112, 114, 122, 123, 166, 188, 202, 씨. 아이. 보라색 안료 19 및 23이 포함된다. 청색을 갖는 안료로는, 예를 들면, 씨. 아이. 청색 안료 1, 2, 15, 15:3, 15:4, 16, 25 및 75가 포함된다. 녹색을 갖는 안료로는, 예를 들면 씨. 아이. 녹색 안료 7 및 36이 포함된다. 흑색을 갖는 안료로는, 예를 들면, 씨. 아이. 흑색 안료 1 및 7이 포함된다. 시판 구입가능한 색상의 안료로는, 예를 들면, 적색 안료 122 및 보라색 안료 19 (뉴저지주 몬트베일 소재의 란스코 컬러스(Lansco Colors) 또는 노쓰캐롤라이나주 샬롯 소재의 바스프 컬러(BASF Color) 또는 노쓰캐롤라이나주 샬롯 소재의 클라리언트 컬러스(Clariant Colors) 또는 오하이오주 신시내티 소재의 선 케미칼(Sun Chemical)로부터 구입가능함), 청색 안료 15:1 (뉴저지주 팬우드 소재의 팬우드 케미칼(Fanwood Chemical)로부터 구입가능함), 청색 안료 15:3, 청색 안료 15:4, 황색 안료 74 및 황색 안료 97 (노쓰캐롤라이나주 샬롯 소재의 바스프 컬러 또는 노쓰캐롤라이나주 샬롯 소재의 클라리언트 컬러스 또는 오하이오주 신시내티 소재의 선 케미칼로부터 구입가능함)이 포함된다. Pigments that can be surface modified in accordance with the present invention include, but are not limited to, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, thioindigo pigments, triphenylmethane lake pigments and oxazine lake pigments . Specifically, as the pigment having a yellow color, for example, children.
적합한 안료로는 또한 카본 블랙이 포함된다. 카본 블랙은 열분해 또는 천연 기체 및 탄화수소 (예컨대 콜 타르(coal tar) 기재의 방향족 오일, 광유, 콜 타르 증류액 및 아세틸렌)의 불완전 연소로부터 유래된 탄소 입자에 대한 일반명이다. 100종 초과의 개별 등급의 카본 블랙이 현재 시판 구입가능하고, 각각은 그 자신만의 구분되는 일군의 특징 및 특성을 갖는다. 임의의 산성 카본 블랙, 중성 카본 블랙 및 알칼리 카본 블랙은 본 발명에 개시된 처리에 유익하게 적용될 수 있다. 여기에는 채널 블랙, 기체 블랙, 램프 블랙, 열 블랙, 아세틸렌 블랙 및 용광로 블랙이 포함된다. 보다 구체적으로, 적합한 카본 블랙에는 채널 블랙이 포함된다. 사용된 카본 블랙의 특질은 평균 입도, 불투명도, 색조, 안정성 등과 같은 분산액의 주요 특성에 대해 영향을 미칠 것이다. 시판 구입가능한 카본 블랙의 예로는, 이들로 한정되지는 않지만, 캐보트(Cabot) (엘프텍스(Elftex) 8, 블랙 펄스(Black Pearls)® 490, 블랙 펄스® 120, 모나크(Monarch)® 120, 모나크® 700, 모나크® 880, 모나크® 1000, 모나크® 1100, 모나크® 1300, 모나크® 1400, 모굴(Mogul)® L, 레갈(Regal)® 99R, 레갈® 250R, 레갈® 300R, 레갈® 330R, 레갈® 400R, 레갈® 500R, 레갈® 660R), 데구사(Degussa) (니펙스(NIPex)® 150 IQ, 니펙스® 150, 프린텍스(Printex)® 55, 프린텍스® 80, 프린텍스® 90, 프린텍스® A, 프린텍스® G, 프린텍스® U, 프린텍스® V, 프린텍스® 140U, 프린텍스® 140V, 퓨렉스(Purex)® LS 35, 코락스(Corax)® HP 160, 써멀 블랙(Thermal Black) N 990, 니펙스® 160 IQ, 니펙스® 90, 스페셜 블랙(Special black) 4, 스페셜 블랙 4A, 스페셜 블랙 5, 스페셜 블랙 6, 스페셜 블랙 100, 스페셜 블랙 250, 컬러 블랙(Color black) FW1, 컬러 블랙 FW2, 컬러 블랙 FW2V, 컬러 블랙 FW18, 컬러 블랙 FW200, 컬러 블랙 S150, 컬러 블랙 S160 및 컬러 블랙 S170), 콜럼비안(Columbian) (라벤(Raven)® 780, 라벤® 5000 UII, 라벤® 1255, 라벤® 2500 U, 라벤® 3600 U, 라벤® 3500, 라벤® 7000, 라벤® 1220 및 라벤® 1225) 및 미쯔비시 가가꾸 가부시끼 가이샤(Mitsubishi Kagaku K.K.) (MA8, MA11, MA77, MA100, MA220, MA230, MA600, MCF88, #10B, #20B, #30, #33, #40, #44, #45, #45L, #50, #55, #95, #260, #900, 970#, #1000, #2200B, #2300, #2350, #2400B, #2650, #2700, #4000B 및 CF9)로부터 구입가능한 것들이 포함된다.Suitable pigments also include carbon black. Carbon black is a common name for carbon particles derived from pyrolysis or incomplete combustion of natural gas and hydrocarbons (for example aromatic oils, mineral oils, coal tar distillates and acetylenes based on coal tar). More than 100 individual grades of carbon black are currently commercially available, each with its own distinct set of features and characteristics. Any of the acidic carbon black, neutral carbon black and alkali carbon black can be advantageously applied to the process disclosed in the present invention. These include channel black, gas black, lamp black, thermal black, acetylene black and blast furnace black. More specifically, suitable carbon blacks include channel black. The properties of the carbon black used will affect the main properties of the dispersion, such as average particle size, opacity, hue, stability, and the like. Examples of commercially commercially available carbon black include, but are not limited to, Cabot (Cabot) (Elf-Tex (Elftex) 8, black pulse (Black Pearls) ® 490, black pulse ® 120, Monarch (Monarch) ® 120, Monarch ® 700, Monarch ® 880, Monarch ® 1000, Monarch ® 1100, Monarch ® 1300, Monarch ® 1400, mogul (mogul) ® L, Regal (Regal) ® 99R, Regal ® 250R, Regal ® 300R, Regal ® 330R, Regal ® 400R, Regal ® 500R, Regal ® 660R), Degussa (Degussa) (your Pecs (NIPex) ® 150 IQ, you Pecs ® 150, Printex (Printex) ® 55, Printex ® 80, Printex ® 90 , Printex ® A, Printex ® G, Printex ® U, Printex ® V, Printex ® 140U, Printex ® 140V, Pew Rex (Purex) ® LS 35, nose flux (Corax) ® HP 160, thermal black (Thermal black) N 990, you Pécs ® 160 IQ, you Pécs ® 90, Special black (Special black) 4, Special black 4A, Special black 5, Special black 6, Special black 100, Special black 250, color block Rack (Color black) FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, and Color Black S170), kolreombi not (Columbian) (Raven (Raven) ® 780, Raven ® 5000 UII, Raven ® 1255, Raven ® 2500 U, Raven ® 3600 U, Raven ® 3500, Raven ® 7000, Raven ® 1220 and Raven ® 1225) and manufactured by Mitsubishi sikki Chemical right or wrong (Mitsubishi Kagaku KK) (MA8, MA11 # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, # 20, # MA, # MA, MA600, MCF88, # 10B, # 20B, 900, 970 #, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700, # 4000B and CF9.
안료는 다양한 입도로 사용가능하다. 일반적으로, 입도가 작을수록 표면적이 더 크고, 표면적이 클수록 친수성 표면 기를 더 고농도로 수용할 수 있다 (이는 수성-기재 매질 중 카본 블랙의 분산성을 극도로 향상시킴). 따라서, 입도는 표면-개질된 안료의 분산성에 영향을 미칠 수 있다. 예를 들면, 본 발명에서 카본 블랙의 평균 1차 입도는 약 50 nm 미만, 특히 약 30 nm 미만, 특히 약 20 nm 미만, 보다 구체적으로 약 10 nm 미만일 수 있다. 카본 블랙 입자의 응집체는 약 200 nm 미만, 특히 약 150 nm 미만, 보다 구체적으로 약 100 nm 미만일 수 있다. 카본 블랙 입자의 표면적은 약 100 m2/g 초과, 특히 약 150 m2/g 초과, 보다 구체적으로 약 200 m2/g 초과일 수 있다. 더 큰 치수를 갖는 안료 입자는 표면 개질 전에 또는 표면 개질 동안 당업자들에게 공지된 임의의 여러 기술을 이용하여 원하는 크기로 분쇄할 수 있다. 이러한 기술에는, 이들로 한정되지는 않지만, 볼 밀, 마찰기, 유동 제트 혼합기, 임펠러 밀, 콜로이드 밀 및 샌드 밀 (예를 들면, 상표명 '수퍼 밀(Super Mill)', '아지테이터 밀(Agitator Mill)', '다이노-밀(Dyno-mill)' 또는 '비즈 밀(Beads Mill)'로 시판되는 것임)이 포함될 수 있다. 밀 매체에는, 이들로 한정되지는 않지만, 유리 비드, 지르코니아 비드 및 스테인레스 스틸 비드가 포함된다. 밀 매체는 약 0.1 mm 내지 약 3 mm, 보다 구체적으로 약 0.01 mm 내지 약 5 mm 크기 범위의 입자를 포함할 수 있다. 카본 블랙이 쉽게 부서지는 경우, 회전 균질화기 또는 초음파 균질화기를 사용하여 입도를 감소시킬 수 있다. 한 실시양태에서, 표면-개질된 블랙 안료는 약 30 nm 미만의 1차 입도로 이루어진 시판 등급의 카본 블랙 안료 및 약 100 m2/g 초과의 표면적을 갖는 약 200 nm 이하의 응집체로부터 제조된다. Pigments can be used in various particle sizes. In general, the smaller the particle size, the larger the surface area, and the larger the surface area, the more hydrophilic surface groups can be accommodated at higher concentrations (which greatly improves the dispersibility of the carbon black in the aqueous-based medium). Thus, the particle size can affect the dispersibility of the surface-modified pigment. For example, in the present invention, the average primary particle size of the carbon black may be less than about 50 nm, especially less than about 30 nm, especially less than about 20 nm, more specifically less than about 10 nm. Aggregates of carbon black particles may be less than about 200 nm, especially less than about 150 nm, more specifically less than about 100 nm. The surface area of the carbon black particles may be greater than about 100 m 2 / g, especially greater than about 150 m 2 / g, more specifically greater than about 200 m 2 / g. Pigment particles with larger dimensions can be ground to a desired size using any of a variety of techniques known to those skilled in the art, either prior to surface modification or during surface modification. These techniques include, but are not limited to, ball mills, rubbing machines, flow jet mixers, impeller mills, colloid mills and sand mills (e.g. under the trade designations "Super Mill", "Agitator Mill), Dyno-mill or Beads Mill, which are commercially available. Mill media include, but are not limited to, glass beads, zirconia beads, and stainless steel beads. Mill media may include particles ranging in size from about 0.1 mm to about 3 mm, more specifically from about 0.01 mm to about 5 mm. If the carbon black is easily broken, the particle size can be reduced by using a rotary homogenizer or an ultrasonic homogenizer. In one embodiment, the surface-modified black pigment is prepared from a commercial grade carbon black pigment having a primary particle size of less than about 30 nm and an aggregate of about 200 nm or less with a surface area of greater than about 100 m 2 / g.
자가-분산성 안료의 제조 이전에, 안료는 질산, 오존, 과산화수소, 퍼설페이트, 하이포할라이트, 또는 이들의 조합과 같은 산화제를 사용하여 산화될 수 있거나 또는 산화되지 않을 수 있다. 차아염소산나트륨을 사용한 카본 블랙의 수성 산화는 미국 특허 제2,439,442호 (1948년 4월 13일에 특허 허여됨) 및 미국 특허 제3,347,632호 (1967년 10월 17일에 특허 허여됨)에 의해 교시되고, 이들 각각은 본원에 참고로 포함된다. 안료의 산화 후, 이어서 화학식 X-S-ZM의 화합물을 본 발명의 방법을 이용하여 안료의 표면에 부착하여, 새로 도입된 표면 전하 기를 보완한다.Prior to the preparation of the self-dispersible pigment, the pigment may or may not be oxidized using an oxidizing agent such as nitric acid, ozone, hydrogen peroxide, persulfate, hypohalites, or combinations thereof. The aqueous oxidation of carbon black using sodium hypochlorite is taught by U.S. Patent No. 2,439,442 (issued April 13, 1948) and U.S. Patent No. 3,347,632 (issued October 17, 1967) , Each of which is incorporated herein by reference. After oxidation of the pigment, the compound of formula X-S-ZM is then attached to the surface of the pigment using the method of the present invention to supplement the newly introduced surface charge.
일부 예에서, 자가-분산성 안료의 제조 이전에, 안료를 습윤화하고, 나노 크기 입자로 밀링하고, 분쇄 보조제를 사용하여 분산시킬 수 있다. 안료는 분쇄 보조제의 도움으로 밀링하기 전에는 분말 또는 습윤 케이크 형태일 수 있다. 밀링은 치환된 중간체와의 반응 전에, 반응 동안 또는 반응 후에 이루어질 수 있다. 부착 반응이 완결된 후에, 분쇄 보조제는 당업자들에게 공지된 정제 방법을 이용하여 제거될 수 있으며, 개질된 안료 및 물을 주로 함유한 분산액을 형성한다. 분쇄 보조제의 예로는, 이들로 한정되지는 않지만, 트리톤(Triton) X-100 (오하이오주 두블린 소재의 애쉬랜드 인크.(Ashland Inc.)로부터 구입가능함), 아이게팔(Igepal) CA-630 (뉴저지주 크랜버리 소재의 로디아(Rhodia)로부터 구입가능함) 및 서피놀(Surfynol) CT 121, 131 및 141 (펜실베니아주 알렌타운 소재의 에어 프로덕츠(Air Products)로부터 구입가능함)이 포함된다. In some instances, prior to the preparation of the self-dispersible pigment, the pigment may be wetted, milled into nanosized particles, and dispersed using a grinding aid. The pigments may be in the form of a powder or wet cake before milling with the aid of a grinding aid. Milling may be effected before, during or after the reaction with the substituted intermediate. After the attachment reaction is complete, the grinding aid can be removed using purification methods known to those skilled in the art, forming a dispersion containing predominantly a modified pigment and water. Examples of grinding aids include, but are not limited to, Triton X-100 (available from Ashland Inc. of Dublin, Ohio), Igepal CA-630 (available from Ashland Inc. of Ohio) (Available from Rhodia, Cranbury, NJ) and
제1 실시양태의 한 예에서, 설포닐 클로라이드를 포함하는 반응성 화합물은 클로로설폰산을 사용하는 클로로설폰화에 의해 카본 블랙과 같은 안료에 부착된다. 산 농도, 반응 온도 및 지속기간의 조합은 얼마나 많은 설포닐 기가 안료의 표면에 부착되는지 결정한다. 한 실시양태에서, 클로로설폰화는 카본 블랙 중량의 5배 양의 클로로설폰산을 사용하여 수행된다.In one example of the first embodiment, a reactive compound comprising a sulfonyl chloride is attached to a pigment such as carbon black by chlorosulfonation using chlorosulfonic acid. The combination of acid concentration, reaction temperature and duration determines how many sulfonyl groups are attached to the surface of the pigment. In one embodiment, the chlorosulfonation is carried out using chlorosulfonic acid in an amount that is five times the weight of the carbon black.
클로로설폰화는 또한 클로로설폰산과 티오닐 클로라이드의 혼합물을 사용하여 수행되어 동일계내 가수분해를 방지할 수 있다. 티오닐 클로라이드의 양은 가수분해 정도를 제어하거나 또는 심지어 가수분해를 완전히 방지하기 위해 매우 다양해질 수 있다. 한 실시양태에서, 클로로설폰화는 클로로설폰산 348 g 및 티오닐 클로라이드 30 g을 사용하여 수행된다. Chlorosulfonation can also be carried out using a mixture of chlorosulfonic acid and thionyl chloride to prevent in situ hydrolysis. The amount of thionyl chloride can be very varied to control the degree of hydrolysis or even completely prevent hydrolysis. In one embodiment, the chlorosulfonation is carried out using 348 g of chlorosulfonic acid and 30 g of thionyl chloride.
산에 대한 안료의 비 (중량비)는 혼합, 전달 용이성 및 비용을 비롯한 운영 효율의 함수로서 주로 결정된다. 안료의 클로로설폰화는 용매를 첨가하지 않고도 클로로설폰산을 과량으로 사용함으로써 달성될 수 있다. 안료에 대한 산의 최소 비가 약 5인 것은 반응 전체에서 양호한 혼합을 제공하기에 적합하다. 매우 과량 (예컨대 약 20의 비율)은 유의한 이점을 생성하지 않으면서, 물질 비용 및 취급 비용 둘다를 상승시킨다. 한 실시양태에서, 클로로설폰산은 약 5배 과량 (w/w)으로 사용된다. 또다른 실시양태에서, 안료 대 클로로설폰화제의 비는 적어도 약 4:1 (w/w)이다. 또다른 실시양태에서, 안료 대 클로로설폰화제의 비는 약 1:20 내지 약 1:1 (w/w)이다. 추가의 실시양태에서, 클로로설폰화제는 약 3:1 내지 약 6:1 (w/w) 비의 클로로설폰산 및 티오닐 클로라이드의 혼합물일 수 있다. The ratio of the pigment to the acid (weight ratio) is mainly determined as a function of operational efficiency, including mixing, ease of transport and cost. Chlorosulfonation of the pigment can be achieved by using an excess of chlorosulfonic acid without addition of a solvent. A minimum ratio of the acid to the pigment of about 5 is suitable to provide good mixing throughout the reaction. A very high amount (e.g., a ratio of about 20) increases both the material cost and the handling cost without creating a significant advantage. In one embodiment, the chlorosulfonic acid is used at about 5-fold excess (w / w). In another embodiment, the ratio of pigment to chlorosulfonating agent is at least about 4: 1 (w / w). In another embodiment, the ratio of pigment to chlorosulfonating agent is from about 1: 20 to about 1: 1 (w / w). In a further embodiment, the chlorosulfonating agent may be a mixture of chlorosulfonic acid and thionyl chloride in a ratio of about 3: 1 to about 6: 1 (w / w).
안료의 클로로설폰화는 약 2일 이하의 기간 동안 승온에서 수행될 수 있다. 클로로설폰화 동안의 반응 온도는 약 140℃ 이상, 특히 약 130℃ 이상, 보다 구체적으로 약 120℃ 이상일 수 있다. 게다가, 클로로설폰화 동안의 반응 온도는 약 60℃ 이하, 특히 약 90℃ 이하, 보다 구체적으로 약 120℃ 이하일 수 있다. 이것은 클로로설폰화 동안의 반응 온도가 약 120℃ 내지 약 130℃, 보다 구체적으로 약 140℃ 이하인 실시양태를 포함한다. 또다른 실시양태에서, 클로로설폰화 동안의 반응 온도는 약 25℃ 내지 약 160℃이다. 일반적으로, 온도가 높을수록 안료의 표면 상에서 바람직한 설포닐 기의 농도를 달성하기 위해 더 짧은 반응 시간이 요구된다. 예를 들면, 반응 온도 140℃에서의 원하는 클로로설폰화에는 약 6시간이 소요될 수 있지만, 80℃에서 동일한 정도의 클로로설폰화는 72시간 초과로 소요되는 것으로 예상될 것이다. 몇몇 실시양태에서, 반응 시간은 약 2시간 이상, 다른 실시양태에서는 약 6시간 이상, 또다른 실시양태에서는 약 24시간 이상일 수 있다. 다른 실시양태에서, 반응 시간은 약 48시간 이하, 다른 실시양태에서는 약 24시간 이하, 또다른 실시양태에서는 약 6시간 이하일 수 있다. 이것은 반응 시간이 약 1시간 내지 약 48시간인 실시양태를 포함한다. 반응 용기의 내용물을 클로로설폰화 동안 교반하여 적절하게 혼합되도록 유지한다. The chlorosulfonation of the pigment can be carried out at elevated temperatures for a period of about 2 days or less. The reaction temperature during the chlorosulfonation may be at least about 140 ° C, in particular at least about 130 ° C, more particularly at least about 120 ° C. In addition, the reaction temperature during the chlorosulfonation can be about 60 캜 or less, particularly about 90 캜 or less, more specifically about 120 캜 or less. This includes embodiments wherein the reaction temperature during the chlorosulfonation is from about 120 캜 to about 130 캜, more specifically about 140 캜 or less. In another embodiment, the reaction temperature during the chlorosulfonation is from about 25 캜 to about 160 캜. In general, the higher the temperature, the shorter the reaction time is required to achieve the desired concentration of the sulfonyl group on the surface of the pigment. For example, the desired chlorosulfonation at a reaction temperature of 140 占 폚 may take about 6 hours, but the same degree of chlorosulfonation at 80 占 폚 is expected to take over 72 hours. In some embodiments, the reaction time may be at least about 2 hours, in other embodiments at least about 6 hours, in yet another embodiment at least about 24 hours. In other embodiments, the reaction time may be up to about 48 hours, in other embodiments up to about 24 hours, in another embodiment up to about 6 hours. This includes embodiments wherein the reaction time is from about 1 hour to about 48 hours. The contents of the reaction vessel are stirred during chlorosulfonation to ensure proper mixing.
클로로설폰화 후에, 반응 혼합물을 물 중에 켄칭할 수 있다. 몇몇 실시양태에서, 반응 혼합물을 약 20℃ 미만의 온도로 냉각시킨 후에 켄칭할 수 있고, 다른 실시양태에서는 약 60℃ 미만의 온도로 냉각시킨 후에 켄칭할 수 있고, 또다른 실시양태에서는 약 90℃ 미만의 온도로 냉각시킨 후에 켄칭할 수 있다. 이것은 반응 혼합물을 약 20℃ 내지 약 90℃의 온도로 냉각시킨 후에 켄칭하는 실시양태를 포함한다. 반응 혼합물이 첨가되는 물은, 예를 들면, 얼음, 냉각 장치 또는 그의 조합을 이용하여 약 10℃의 온도 이하가 될 수 있다. 한 실시양태에서, 켄칭 온도를 약 0℃ 내지 약 5℃에서 유지하여 반응성 설포닐 클로라이드 중간체를 보존한다. 클로로설폰화된 생성물 (습윤 케이크로 언급됨)을 여과에 의해 물로부터 단리하고, 잉여의 반응물 및 수용성 생성물이 제거되도록 세척할 수 있다. 이것은 <5℃ 물로 세척할 수 있다. After the chlorosulfonation, the reaction mixture can be quenched into water. In some embodiments, the reaction mixture may be quenched after cooling to a temperature of less than about 20 占 폚, and in other embodiments may be quenched after cooling to a temperature of less than about 60 占 폚; in another embodiment, Lt; / RTI > and then quenched. This includes embodiments wherein the reaction mixture is quenched after cooling to a temperature of from about 20 [deg.] C to about 90 [deg.] C. The water to which the reaction mixture is added can be at or below about 10 캜 using, for example, ice, a cooling device, or a combination thereof. In one embodiment, the quenching temperature is maintained at about 0 캜 to about 5 캜 to preserve the reactive sulfonyl chloride intermediate. The chlorosulfonated product (referred to as wet cake) can be isolated from the water by filtration and washed to remove excess reactants and water-soluble products. It can be washed with <5 ° C water.
그 후, 안료 반응성 중간체는 산으로 다시 가수분해되는 것을 방지하는 유기 기를 포함하는 1개 이상의 이차 화합물로 치환된다. 한 실시양태에서, 안료 반응성 중간체는 이차 화합물과의 반응에 즉시 사용될 수 있다. 예를 들면, 반응성 설포닐 클로라이드 기를 갖는 카본 블랙은 아미노 및 산성 말단 기를 함유한 유기 화합물과 즉시 반응할 수 있다. 유기 기를 포함하는 이차 화합물은 안료에 대한 원하는 최종 적용에 따라 선택될 수 있다. The pigment reactive intermediate is then substituted with one or more secondary compounds comprising an organic group that prevents it from being hydrolyzed back to the acid. In one embodiment, the pigment reactive intermediate can be used immediately for reaction with the secondary compound. For example, carbon black having a reactive sulfonyl chloride group can react immediately with organic compounds containing amino and acidic end groups. The secondary compound comprising an organic group can be selected according to the desired end application for the pigment.
안료 반응성 중간체는 산성 pH (약 2 내지 약 5) 범위의 이차 화합물과 반응할 수 있다. 산성 pH 범위는 반응성 화합물의 안정성을 상승시키고, 가수분해 및 자가-축합과 같은 바람직하지 않은 반응의 정도를 감소시킨다. 반응성 화합물은 아미노 페놀이 유기 기로서 사용되는 경우에도 1급 아민과 같은 염기와 우선적으로 반응한다. 이러한 반응은 당업자들에게 공지된 pH, 온도 및 희석과 같은 반응 조건의 적절한 선택에 의해 아미노 말단에 주로 지정될 수 있다. 예를 들면, pH는 약 2 내지 약 5일 수 있고, 온도는 약 0℃ 내지 약 5℃일 수 있다. 또다른 실시양태에서, 안료 반응성 중간체를 이차 화합물과 반응시키는 동안, 비드 밀에서 반응을 수행함으로써 안료의 입도를 감소시킬 수 있다. 이차 화합물이 부식성이므로, 강산 및 강염기에 대해 저항성인 구조의 적절한 물질을 선택하여 생성물 내로의 금속 침출을 방지할 수 있다.The pigment reactive intermediate may react with a secondary compound in the acidic pH range (about 2 to about 5). The acidic pH range increases the stability of the reactive compound and reduces the extent of undesirable reactions such as hydrolysis and self-condensation. The reactive compound preferentially reacts with bases such as primary amines even when aminophenols are used as organic groups. Such reactions can be predominantly assigned to the amino terminus by appropriate selection of reaction conditions such as pH, temperature and dilution known to those skilled in the art. For example, the pH may be from about 2 to about 5, and the temperature may be from about 0 캜 to about 5 캜. In another embodiment, during the reaction of the pigment reactive intermediate with the secondary compound, the particle size of the pigment can be reduced by performing the reaction in a bead mill. Since the secondary compound is corrosive, it is possible to select a suitable material of a structure resistant to strong acids and strong bases to prevent metal leaching into the product.
안료 반응성 중간체 및 이차 화합물 간의 반응은 혼합하면서 약 2시간 내지 약 4시간의 기간 동안 수행할 수 있다. 한 실시양태에서, 혼합물을 약 60℃ 내지 약 90℃의 승온으로 가열함으로써 반응을 완결할 수 있다. The reaction between the pigment reactive intermediate and the secondary compound may be carried out for a period of from about 2 hours to about 4 hours while mixing. In one embodiment, the reaction can be completed by heating the mixture to an elevated temperature from about 60 캜 to about 90 캜.
제1 실시양태의 또다른 예로는, 이들에 한정되지는 않지만, 반응성 기 X-Y를 안료의 표면에 부착시키는 단계; 및 그 후, Y를 유기 기질 N-S-ZM으로 치환시켜 X-N-S-ZM이 부착된 표면 개질된 안료를 형성하는 단계 (여기서, X는 설포닐, 포스포릴 또는 1,3,5-트리아지닐 기이고; Y는 할로겐 이탈기이고; N은 염기성 친핵성 기이고; S는 유기 기이고; ZM은 이온화 말단기임)를 포함할 수 있는, 표면을 갖는 안료 개질 방법이 포함될 수 있다. 대부분의 안료 표면은 개질되어 액상 겔을 형성할 수 있다. 그 후, 액상 겔은 과량의 미처리된 안료 및 물과 함께 밀링되어 안정한 안료 수분산액을 형성할 수 있다. 대부분의 안료 표면을 개질하는 한 예에는, 이들로 한정되지는 않지만, 약 90℃ 이상의 온도에서 약 1시간 이상 동안 안료를 클로로설폰화시켜, 클로로설폰화된 안료 또는 안료 설포닐 클로라이드를 형성하는 것이 포함된다. Other examples of the first embodiment include, but are not limited to, attaching a reactive group X-Y to the surface of the pigment; And thereafter replacing Y with an organic substrate NS-ZM to form a surface modified pigment with XNS-ZM attached, wherein X is a sulfonyl, phosphoryl or 1,3,5-triazinyl group; Y is a halogen leaving group, N is a basic nucleophilic group, S is an organic group, and ZM is an ionizing end group). Most pigment surfaces can be modified to form liquid gels. The liquid gel can then be milled with excess untreated pigment and water to form a stable pigment water dispersion. An example of modifying most pigment surfaces includes, but is not limited to, chlorosulfonating the pigment for at least about one hour at a temperature of at least about 90 캜 to form a chlorosulfonated pigment or pigment sulfonyl chloride .
제2 실시양태의 한 예에서, 시아누릴 기를 포함하는 반응성 화합물은 유기 기를 포함하는 이차 화합물로 치환된다. 이어서, 치환된 반응성 중간체 -X-S-ZM은 시아누릭 클로라이드를 사용함으로써 카본 블랙과 같은 안료에 부착된다. pH, 반응 온도 및 지속기간의 조합은 얼마나 많은 기가 안료의 표면에 부착되는지 결정한다. 한 실시양태에서, 반응은 카본 120 g 당 시아누릭 클로라이드 52 g을 사용하여 수행된다. 또다른 실시양태에서, 반응은 카본 40 g 당 시아누릭 클로라이드 15 g을 사용하여 수행된다.In one example of the second embodiment, the reactive compound comprising a cyano group is substituted with a secondary compound comprising an organic group. Substituted reactive intermediate -X-S-ZM is then attached to a pigment such as carbon black by using cyanuric chloride. The combination of pH, reaction temperature and duration determines how many glues are attached to the surface of the pigment. In one embodiment, the reaction is carried out using 52 g of cyanuric chloride per 120 g of carbon. In another embodiment, the reaction is carried out using 15 g of cyanuric chloride per 40 g of carbon.
몇몇 실시양태에서, 유기 기를 포함하는 이차 화합물, 시아누릭 클로라이드, 물, 얼음 및 염기의 슬러리가 제조된다. 유기 기를 포함하는 이차 화합물은 안료에 대한 원하는 최종 적용에 따라 선택될 수 있다.In some embodiments, a slurry of a secondary compound comprising an organic group, cyanuric chloride, water, ice, and base is prepared. The secondary compound comprising an organic group can be selected according to the desired end application for the pigment.
제3 실시양태의 예에서, 시아누릴 기를 포함하는 반응성 화합물은 동일하거나 상이할 수 있는 2개의 유기 기를 포함하는 이차 화합물로 치환된다. 이어서, 치환된 2개의 반응성 중간체 X-S-ZM 및 X-S2-Z2M2는 시아누릭 클로라이드를 사용함으로써 카본 블랙과 같은 안료에 부착된다. pH, 반응 온도 및 지속기간의 조합은 얼마나 많은 기가 안료의 표면에 부착되는지 결정한다. 이 방법은 유기 기를 포함하는 이차 화합물, 시아누릭 클로라이드, 물, 얼음 및 염기의 슬러리와 먼저 반응시킴으로써 순차적으로 수행될 수 있다. 유기 기를 포함하는 상이한 이차 화합물, 시아누릭 클로라이드, 물, 얼음, 산 및 염기의 제2 슬러리는 상기 과정을 완결하기 위해 사용된다.In an example of the third embodiment, the reactive compound comprising a cyano group is substituted with a secondary compound comprising two organic groups which may be the same or different. Substituted two reactive intermediates X-S-ZM and X-S2-Z2M2 are then attached to a pigment such as carbon black by using cyanuric chloride. The combination of pH, reaction temperature and duration determines how many glues are attached to the surface of the pigment. The process may be carried out sequentially by first reacting with a slurry of a secondary compound comprising an organic group, cyanuric chloride, water, ice and base. A second slurry of different secondary compounds comprising organic groups, cyanuric chloride, water, ice, acid and base is used to complete the process.
시아누릴 클로라이드 대 이차 화합물의 비는 전형적으로는 화학량론에 따라 결정되고, 농도는 양호한 혼합을 허용하도록 제어된다. 시아누릭 클로라이드 및 이차 화합물 간의 반응은 혼합하면서 약 2시간 내지 약 4시간의 기간 동안 수행할 수 있다.The ratio of cyanuric chloride to secondary compound is typically determined by stoichiometry and the concentration is controlled to allow good mixing. The reaction between the cyanuric chloride and the secondary compound can be carried out for a period of from about 2 hours to about 4 hours while mixing.
제4 실시양태의 한 예에서, 시아누릴 클로라이드 중의 모든 반응성 염소를 화학량론 (3개 모두의 염소를 치환시키기 위해서는 3 당량) 및 온도 (약 90℃ 이상의 온도)를 조작함으로써 이차 화합물 또는 이차 화합물의 혼합물로 치환하고, 그 후 안료와 반응시킨다. 이 반응은 치환된 트리아진을 형성하고, 상기 치환된 트리아진은 안료의 표면에 부착될 수 있다. 이차 화합물의 혼합물은 1, 2 또는 3종의 상이한 이차 화합물을 포함할 수 있다. 이러한 예에서, 퍼설페이트 잔기와 같은 라디칼 개시제는 부착 방법을 불균등화시키고 용이하게 하기 위해 사용된다. 몇몇 실시양태에서, 반응은 약 25℃ 내지 약 90℃의 온도에서 수행될 수 있다. 또다른 실시양태에서, 안료는 치환된 트리아진과 안료와의 반응 전에, 반응 동안 또는 반응 후에 약 100 nm 미만으로 밀링될 수 있다. In one example of the fourth embodiment, by manipulating all of the reactive chlorine in the cyanuric chloride with stoichiometry (three equivalents to replace all three chlorines) and temperature (temperatures above about 90 占 폚) Substituted with a mixture, and then reacted with the pigment. This reaction forms a substituted triazine, and the substituted triazine can be attached to the surface of the pigment. The mixture of secondary compounds may comprise one, two or three different secondary compounds. In this example, a radical initiator such as a persulfate moiety is used to disproportionate and facilitate the attachment method. In some embodiments, the reaction may be carried out at a temperature from about 25 [deg.] C to about 90 [deg.] C. In another embodiment, the pigment can be milled to less than about 100 nm before, during, or after the reaction of the substituted triazine with the pigment.
안료는 이 "시약"과 혼합되어 분산액을 생성한다. 상이한 이차 화합물을 함유한 2개의 슬러리가 존재하는 실시양태에서, 안료를 순차적으로 슬러리와 혼합한다. 분산액의 온도는 약 1시간 내지 약 2시간의 기간 동안 약 0℃ 내지 약 15℃에서 유지될 수 있다. 이어서, 반응성 화합물 (예를 들면, 치환된 트리아진) 분산액 및 안료의 혼합물을 약 2일 이하 기간 동안 승온으로 가열한다. 칼륨 퍼설페이트와 같은 자유 라디칼 개시제를 첨가하여 반응을 촉진할 수 있다. 반응 온도는 약 40℃ 이상, 특히 약 50℃ 이상, 보다 구체적으로 약 60℃ 이상일 수 있다. 게다가, 반응 온도는 약 90℃ 이하, 특히 약 80℃ 이하, 보다 구체적으로 약 60℃ 이하일 수 있다. 이것은 반응 온도가 약 50℃ 내지 약 60℃, 보다 구체적으로 90℃ 이하인 실시양태를 포함한다. 일반적으로, 50℃ 초과의 온도는 자유 라디칼 개시제가 효과적이도록 하기 위해 필요하다. 이것은 반응 시간이 약 16시간 내지 약 24시간인 실시양태를 포함한다. 반응 용기의 내용물을 반응 동안 교반하여 적절하게 혼합되도록 한다. 개질된 안료를 여과하여 잉여의 반응물 및 불순물을 제거할 수 있다. The pigment is mixed with this "reagent" to produce a dispersion. In embodiments where there are two slurries containing different secondary compounds, the pigments are sequentially mixed with the slurry. The temperature of the dispersion can be maintained at about 0 캜 to about 15 캜 for a period of about 1 hour to about 2 hours. The mixture of the reactive compound (e.g., substituted triazine) dispersion and the pigment is then heated to elevated temperature for a period of about 2 days or less. A free radical initiator such as potassium persulfate may be added to facilitate the reaction. The reaction temperature may be at least about 40 ° C, in particular at least about 50 ° C, more specifically at least about 60 ° C. In addition, the reaction temperature may be about 90 캜 or less, particularly about 80 캜 or less, more specifically about 60 캜 or less. This includes embodiments wherein the reaction temperature is from about 50 째 C to about 60 째 C, more specifically less than or equal to 90 째 C. In general, temperatures above 50 DEG C are needed to ensure that the free radical initiator is effective. This includes embodiments wherein the reaction time is from about 16 hours to about 24 hours. The contents of the reaction vessel are allowed to stir and mix appropriately during the reaction. The modified pigment can be filtered to remove excess reactants and impurities.
한 실시양태에서, 반응성 화합물 (예컨대 시아누릭 클로라이드)은 산성 pH (약 2 내지 약 5) 범위에서 이차 화합물과 반응한다. 산성 pH 범위는 반응성 화합물의 안정성을 상승시키고, 가수분해 및 자가-축합과 같은 바람직하지 않은 반응의 정도를 감소시킨다. 반응성 화합물은 아미노 페놀이 유기 기로서 사용되는 경우에도 1급 아민과 같은 염기와 우선적으로 반응한다. 이러한 반응은 당업자들에게 공지된 pH, 온도 및 희석과 같은 반응 조건의 적절한 선택에 의해 아미노 말단에 주로 지정될 수 있다. 예를 들면, pH는 약 2 내지 약 5일 수 있고, 온도는 약 0℃ 내지 약 5℃일 수 있다. In one embodiment, the reactive compound (e.g., cyanuric chloride) reacts with the secondary compound in the acidic pH range (about 2 to about 5). The acidic pH range increases the stability of the reactive compound and reduces the extent of undesirable reactions such as hydrolysis and self-condensation. The reactive compound preferentially reacts with bases such as primary amines even when aminophenols are used as organic groups. Such reactions can be predominantly assigned to the amino terminus by appropriate selection of reaction conditions such as pH, temperature and dilution known to those skilled in the art. For example, the pH may be from about 2 to about 5, and the temperature may be from about 0 캜 to about 5 캜.
임의로, 안료를 기 -X-S-ZM과 반응시키는 동안, 비드 밀에서 반응을 수행함으로써 안료의 입도를 감소시킬 수 있다. 이차 화합물이 부식성이므로, 강산 및 강염기에 대해 저항성인 구조의 적절한 물질을 선택하여 생성물 내로의 금속 침출을 방지할 수 있다.Optionally, the pigment may be reduced in particle size by carrying out the reaction in a bead mill while allowing the pigment to react with the group -X-S-ZM. Since the secondary compound is corrosive, it is possible to select a suitable material of a structure resistant to strong acids and strong bases to prevent metal leaching into the product.
산 유도체를 포함하는 2급 기 또는 반응성 화합물과 안료와의 반응은 반응 혼합물의 pH를 낮출 수 있는 산성 표면 기를 생성할 수 있다. pH의 감소는 치환 동안 개질된 안료 분산액 또는 반응성 화합물 및 이차 화합물의 슬러리를 불안정화시키고, 또한 점도를 증가시킬 수 있다. 따라서, 필요에 따라 염기성 시약으로의 치환 전에 및 치환 동안 pH를 조정할 수 있다. 치환 동안 반응 혼합물의 pH는 약 7 이상, 특히 약 8 이상, 보다 구체적으로 약 9 이상일 수 있다. pH는, 예를 들면, 염기의 첨가를 비롯한 당업계에 임의의 공지된 방법에 의해 조정될 수 있다. 적합한 염기로는, 이들로 한정되지는 않지만, 알칼리 수산화물 및 칼슘 무함유 알칼리 수산화물 (예를 들면, NaOH, KOH, LiOH, NH4OH), 알칼리 탄산염 및 중탄산염 (예를 들면, NaHCO3, KHCO3) 및 유기 염기 (예를 들면, 디메틸에탄올 아민 및 트리에탄올 아민)가 포함된다. 특히, 적합한 pH 조절제는 칼슘 무함유 수산화나트륨이다.Reaction of the pigment with a secondary or reactive compound containing an acid derivative can produce an acidic surface group that can lower the pH of the reaction mixture. Decreasing the pH can destabilize the slurry of modified pigment dispersions or reactive compounds and secondary compounds during displacement and also increase the viscosity. Thus, the pH can be adjusted before and during replacement with a basic reagent, if necessary. The pH of the reaction mixture during the substitution may be at least about 7, in particular at least about 8, more particularly at least about 9. The pH can be adjusted by any known method in the art, including, for example, addition of a base. Suitable bases include, but are not limited to, alkali hydroxides and calcium-free alkali hydroxide (e.g., NaOH, KOH, LiOH, NH 4 OH), alkali carbonate and bicarbonate (e.g., NaHCO 3, KHCO 3 ) And organic bases (e.g., dimethylethanolamine and triethanolamine). In particular, a suitable pH adjusting agent is calcium-free sodium hydroxide.
표면 개질된 안료Surface modified pigment
상기 기재된 반응이 완료된 후, 자가-분산성 안료는 반응 혼합물로부터 건조 분말로서 단리될 수 있다. 생성된 개질된 안료는 당업자에게 공지된 많은 기술을 이용하여 정제함으로써 반응하지 않은 원료, 부산물 염 및 다른 반응 불순물을 제거할 수 있다. 정제 기술에는 여과, 원심분리, 또는 이 둘의 조합이 포함될 수 있으나, 이들로 한정되지는 않는다. 개질된 안료는 또한, 예를 들면 증발에 의해 단리될 수 있거나, 또는 이는 당업자에게 공지된 기술을 이용한 여과 및 건조에 의해 회수될 수 있다.After completion of the reaction described above, the self-dispersible pigment may be isolated as a dry powder from the reaction mixture. The resulting modified pigment can be purified using a number of techniques known to those skilled in the art to remove unreacted raw materials, by-product salts, and other reactive impurities. Purification techniques may include, but are not limited to, filtration, centrifugation, or a combination of the two. The modified pigment may also be isolated, for example by evaporation, or it may be recovered by filtration and drying using techniques known to those skilled in the art.
별법으로, 자가-분산성 안료는 농축 수성 안료 분산액으로서 전달될 수 있다. 본 발명의 자가-분산성 안료의 분산액을 정제하여, 제조 공정의 결과로서의 분산액 중에 공존할 수 있는 유기 및 무기 불순물 및 다른 바람직하지 않은 유리 종(free species)을 제거할 수 있다. 정제 기술에는 물 세척, 역삼투 및 한외여과가 포함될 수 있으나, 이들로 한정되지는 않는다. 몇몇 실시양태에서, 용해된 불순물은 10% 고체로 조정된 공급 샘플의 클로라이드 및 설페이트 함량이 약 150 ppm 미만, 특히 약 100 ppm 미만, 보다 구체적으로는 약 25 ppm 미만이 될 때까지 한외여과로 제거될 수 있다. 필요한 경우, 정제하기 전에 분산액의 pH를 조정할 수 있다. 충분한 양의 산 또는 염기를 첨가하여, 분산액의 pH를 약 7 이상, 특히 약 8 이상, 보다 구체적으로는 약 9 이상으로 조정할 수 있다. 본 발명은 분산액의 pH가 약 7 내지 약 9인 실시양태를 포함한다. 분산액은 원한다면 물의 일부를 제거하여 농축될 수 있다. 몇몇 실시양태에서, 분산액은 약 8% 이상의 고체로, 다른 실시양태에서는 약 14% 이상의 고체로, 또다른 실시양태에서는 약 20% 이상의 고체로 농축된다. 본 발명은 분산액이 약 8% 내지 약 16% 고체로 농축되는 실시양태를 포함한다. 다른 실시양태에서, 분산액은 약 10% 이상의 고체로, 다른 실시양태에서는 약 18% 이상의 고체로, 또다른 실시양태에서는 약 20% 이상의 고체로 농축된다. 본 발명은 분산액이 약 14% 내지 약 8% 고체로 농축되는 실시양태를 포함한다.Alternatively, the self-dispersible pigment may be delivered as a concentrated aqueous pigment dispersion. The dispersion of the self-dispersible pigment of the present invention can be purified to remove organic and inorganic impurities and other undesirable free species that may coexist in the dispersion as a result of the manufacturing process. Purification techniques may include, but are not limited to, water washing, reverse osmosis and ultrafiltration. In some embodiments, the dissolved impurities are removed by ultrafiltration until the chloride and sulfate content of the 10% solids adjusted feed sample is less than about 150 ppm, especially less than about 100 ppm, and more specifically less than about 25 ppm. . If desired, the pH of the dispersion can be adjusted prior to purification. A sufficient amount of acid or base can be added to adjust the pH of the dispersion to about 7 or higher, especially about 8 or higher, more specifically about 9 or higher. The present invention includes embodiments wherein the pH of the dispersion is from about 7 to about 9. The dispersion may be concentrated by removing a portion of the water if desired. In some embodiments, the dispersion is concentrated to at least about 8% solids, in other embodiments at least about 14% solids, and in other embodiments at least about 20% solids. The present invention includes embodiments wherein the dispersion is concentrated to about 8% to about 16% solids. In another embodiment, the dispersion is concentrated to at least about 10% solids, in other embodiments at least about 18% solids, and in another embodiment at least about 20% solids. The present invention encompasses embodiments wherein the dispersion is concentrated to about 14% to about 8% solids.
또한, 미생물의 성장을 억제하기 위해 분산액에 살생제를 첨가할 수 있다. 적합한 살생제의 예에는 나트륨 벤조에이트, 펜타클로로페놀 나트륨, 2-피리딘티올-1-옥사이드 나트륨, 나트륨 소르베이트, 나트륨 데히드로아세테이트, 벤즈이소티아졸리논, 1,2-디벤조티아졸린-3-온, 메틸이소티아졸리논 및 클로로메틸이소티아졸리논이 포함되나, 이들로 한정되지는 않는다. 상업적으로 입수가능한 살생제에는 프록셀(Proxel)® CRL, 프록셀® BDN, 프록셀® GXL, 프록셀® XL-2 및 프록셀® TN (조지아주 스미르나 소재의 아치 케미칼즈(Arch Chemicals)로부터 입수가능함), 및 엑스빙스(XBINX)® (오하이오주 신시내티 소재의 PMC 스페셜티즈 그룹, 인크.(PMC Specialties Group, Inc.)로부터 입수가능함)가 포함된다. 전형적으로는, 소량의 살생제, 예컨대 0.05 내지 5 중량%, 특히 0.1 내지 1 중량%, 보다 구체적으로는 0.2 내지 0.4 중량%의 살생제가 분산액 중에 사용된다. 본 발명은 0.3 중량%의 살생제를 포함한다.In addition, a biocide may be added to the dispersion to inhibit the growth of microorganisms. Examples of suitable biocides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazoline- -Methyl isothiazolinone, and chloromethyl isothiazolinone. ≪ / RTI > Is a commercially available biocide from Proxel (Proxel) ® CRL, Proxel ® BDN, Proxel ® GXL, Proxel ® XL-2 and Proxel ® TN (George Arch Chemicals of very Smyrna material's (Arch Chemicals) retrieving possible), and X is included Savings establishments (XBINX) ® (PMC Special Tees group of Cincinnati, Ohio, Inc.. (PMC Specialties group, Inc.) obtained from the available). Typically, small amounts of biocides, such as 0.05 to 5 wt%, especially 0.1 to 1 wt%, more particularly 0.2 to 0.4 wt%, of the biocide are used in the dispersion. The present invention comprises 0.3% by weight of biocide.
또한, 분산액에 유동성 및 안정성을 부여하기 위해 작용제를 첨가할 수 있다. 이러한 작용제의 예는 미국 특허 제5,059,248호 (1991년 10월 22일에 특허 허여됨), 미국 특허 제5,591,455호 (1997년 1월 7일에 특허 허여됨) 및 미국 특허 제5,595,592호 (1997년 1월 21일에 특허 허여됨)에서 찾아볼 수 있다 (이들은 각각 참고로 본원에 포함됨). 그 예에는 선형 지방족 치환된 글리신 화합물 및 그의 염이 포함되나, 이들로 한정되지는 않는다. 본원에 사용된 용어 "선형 지방족 치환된 글리신"은 글리신의 아미노기가 선형 지방족 기로 치환된 글리신 화합물을 나타낸다. 본 발명의 실행에 사용될 수 있는 이러한 유형의 작용제의 예시로는 에틸렌 디아민 테트라아세트산, 니트릴로 트리아세트산, 디에틸렌 트리아민 펜타아세트산, 히드록시에틸렌 디아민 트리아세트산, 디히드록시에틸 글리신, 이미노디아세트산 및 에탄올 디글리신 및 알칼리 금속 (예를 들면, 나트륨), 알칼리 토금속 (예를 들면, 칼슘) 및 그의 암모늄 염이 있다. 또한, 당업자에게 공지되어 있는 다른 유사한 선형 지방족 치환된 글리신 화합물 및 그의 염이 사용될 수 있다. 몇몇 실시양태에서, 상기 언급한 에틸렌 디아민 테트라아세트산의 염이 그의 유효성, 비용 효율성 및 비독성으로 인해 사용된다. 몇몇 실시양태에서, 이들 작용제는 분산액 조성물 중 안료의 대략 0.5 내지 3.5 중량%, 바람직하게는 약 1.5 내지 2.5 중량%를 구성할 수 있다.Agents can also be added to impart fluidity and stability to the dispersion. Examples of such agents are described in U.S. Patent No. 5,059,248 (issued October 22, 1991), U.S. Patent No. 5,591,455 (issued January 7, 1997) and U.S. Patent No. 5,595,592 Issued on May 21) (each of which is incorporated herein by reference). Examples include, but are not limited to, linear aliphatic substituted glycine compounds and salts thereof. As used herein, the term "linear aliphatic substituted glycine" refers to a glycine compound in which the amino group of the glycine is substituted with a linear aliphatic group. Examples of this type of agent that can be used in the practice of the present invention include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, iminodiacetic acid, and Ethanol diglycine and an alkali metal (for example, sodium), an alkaline earth metal (for example, calcium), and an ammonium salt thereof. Other similar linear aliphatically substituted glycine compounds and salts thereof known to those skilled in the art may also be used. In some embodiments, the above-mentioned salts of ethylenediaminetetraacetic acid are used due to their effectiveness, cost effectiveness and non-toxicity. In some embodiments, these agents may constitute from about 0.5 to 3.5% by weight, preferably from about 1.5 to 2.5% by weight of the pigment in the dispersion composition.
분산액은 필요에 따라 분산액의 지정된 최종 용도를 위해 필터 카트리지를 통해 여과될 수 있다. 몇몇 실시양태에서, 필터 카트리지의 공칭 기공 크기가 약 5 ㎛ 이하, 특히 약 1 ㎛ 이하, 특히 약 0.5 ㎛ 이하, 보다 구체적으로 약 0.2 ㎛ 이하이다. The dispersion may optionally be filtered through a filter cartridge for a specified end use of the dispersion. In some embodiments, the filter cartridge has a nominal pore size of about 5 占 퐉 or less, particularly about 1 占 퐉 or less, particularly about 0.5 占 퐉 or less, more specifically about 0.2 占 퐉 or less.
분말 및 분산액 이외에도, 자가-분산성 안료는 또한 물로 습윤된 프레스케이크로서 단리될 수 있다. 프레스케이크 형태에서, 자가-분산성 안료는 건조 형태로까지 응집되지 않고, 따라서 자가-분산성 안료는 사용시에 (예컨대, 잉크의 제조에서) 분쇄와 같은 것을 필요로 하지 않는다.In addition to powders and dispersions, self-dispersible pigments may also be isolated as a wet cake wet pressed cake. In the form of a press cake, the self-dispersible pigment does not aggregate to the dry form and therefore the self-dispersible pigment does not require such as pulverization in use (e.g. in the manufacture of ink).
원한다면, 부착/치환 방법의 결과로서의 표면-개질기와 회합된 전하-균형 반대이온은 공지되어 있는 이온-교환 기술, 예컨대 한외여과, 역삼투, 중간체로서 산 형태로의 전환 등을 이용하여, 적어도 부분적으로 치환되거나, 적합한 염기 또는 염 형태를 사용하여 변화되거나, 또는 다른 적합한 양이온으로 교환 또는 치환될 수 있다. 반대이온의 예에는 알칼리 금속 이온 (예를 들면, Na+, K+ 및 Li+), NR1R2R3H+ (여기서, R1, R2 및 R3은 독립적으로 H, 또는 비치환 또는 치환될 수 있는 C1-C5 알킬 기일 수 있음) 및 이들의 조합 (예를 들면, 테트라에틸암모늄 이온 (TEA), 테트라메틸암모늄 이온 (TMA), 에탄올암모늄 이온, 트리에탄올암모늄 이온, 테트라부틸암모늄 이온 등)이 포함되나, 이들로 한정되지는 않는다.If desired, the charge-balancing counterion associated with the surface-reforming agent as a result of the attachment / substitution process can be at least partially converted to an acid by use of known ion-exchange techniques such as ultrafiltration, reverse osmosis, Or may be exchanged using a suitable base or salt form, or exchanged or substituted with other suitable cations. Examples of counterions include alkali metal ions (e.g. Na + , K + and Li + ), NR 1 R 2 R 3 H + , wherein R 1 , R 2 and R 3 are independently H, or can be C 1 -C 5 alkyl date which may be substituted), and a combination thereof (e.g., tetraethyl ammonium ion (TEA), tetramethylammonium ion (TMA), ethanol ammonium ion, a triethanol ammonium ion, tetrabutyl Ammonium ions, and the like).
개질된 안료의 특성Properties of modified pigments
자가-분산성 안료는 설폰산 또는 카르복실산 기가 부착된 안료 입자에서 기대되는 것에 비해 장기간 및 고온 안정성, 더 높은 수견뢰성 및 하이라이터 견뢰성(fastness) 중 적어도 하나를 나타낼 수 있고, 고속 분사 적용에 사용하기 적합한 입도 분포를 갖는다.The self-dispersible pigment may exhibit at least one of long-term and high-temperature stability, higher waterfastness and high writer fastness as compared to that expected in pigment particles with sulfonic acid or carboxylic acid groups, Has a particle size distribution suitable for use in application.
자가-분산성 안료는 하기 특성을 가질 수 있다. 개질된 안료의 고체 비(%)는 약 8 내지 16일 수 있다.The self-dispersible pigment may have the following properties. The solids ratio (%) of the modified pigment may be from about 8 to about 16.
개질된 안료 분산액의 pH는 약 5 내지 약 10일 수 있다.The pH of the modified pigment dispersion may be from about 5 to about 10.
개질된 안료 분산액의 점도는 약 1 내지 약 10 cps, 특히 약 1.3 내지 약 7.6 cps일 수 있다.The viscosity of the modified pigment dispersion may be from about 1 to about 10 cps, especially from about 1.3 to about 7.6 cps.
개질된 안료 분산액의 표면 장력은 약 39 내지 약 72 dyne/cm일 수 있다.The surface tension of the modified pigment dispersion may be from about 39 to about 72 dyne / cm.
개질된 안료 분산액 중 Na 및 K의 양은 새롭게 부착된 음이온성 기질 (Na/K 형태로서 술파닐산, 또는 4-아미노페놀 또는 4-아미노벤조산)의 측정치일 수 있다. Na의 양은 약 100 내지 약 6500 ppm일 수 있고, K의 양은 약 30 내지 약 1200 ppm일 수 있다.The amount of Na and K in the modified pigment dispersion may be a measure of the newly attached anionic substrate (sulfanilic acid, or 4-aminophenol or 4-aminobenzoic acid as Na / K form). The amount of Na can be about 100 to about 6500 ppm, and the amount of K can be about 30 to about 1200 ppm.
개질된 안료 분산액 중 S 함량의 증가는 설포닐기의 도입 및/또는 설폰화된 기질 예컨대, 설파닐산 (이들로 한정되지는 않음)의 부착에 인한 것일 수 있다. 개질된 안료 중 S의 양은 약 50 ppm 내지 약 2600 ppm일 수 있다. 한 실시양태에서, 개질된 안료 중 S의 양은 4-아미노벤조산 및 4-아미노페놀 부착에 대해 약 50 ppm일 수 있다. 또다른 실시양태에서, 개질된 안료 중 S의 양은 설파닐산이 설폰 결합을 통해 안료에 부착된 경우에 약 1700 ppm일 수 있다.The increase in the S content in the modified pigment dispersion may be due to the introduction of a sulfonyl group and / or the attachment of a sulfonated substrate such as, but not limited to, sulfanilic acid. The amount of S in the modified pigment may be from about 50 ppm to about 2600 ppm. In one embodiment, the amount of S in the modified pigment may be about 50 ppm for 4-aminobenzoic acid and 4-aminophenol attachment. In another embodiment, the amount of S in the modified pigment can be about 1700 ppm when the sulfanilic acid is attached to the pigment through a sulfone bond.
개질된 안료의 적용Application of modified pigments
본 발명에 따른 자가-분산성 안료는 수많은 최종 용도 적용에 사용될 수 있다. 이들 용도에는 코팅, 페인트, 종이, 접착제, 라텍스, 토너, 직물, 섬유, 플라스틱 및 잉크가 포함되나, 이들로 한정되지는 않는다. 구체적인 예에는 종이, 직물, 섬유, 금속 데코 및 플라스틱, 우드 스테인, 기록 기구, 및 컬러 필터용 인쇄 잉크가 포함되나, 이들로 한정되지는 않는다. 특히, 본 발명의 방법에 의해 제조된 자가-분산성 안료는 인쇄 적용 및 우드 스테인의 용도에 잘 적합화되어 있다. 한 실시예에서, 본 발명의 안료를 도입한 잉크젯 잉크는 잉크젯 사진 프린터에서의 고품질 인쇄에 유용할 수 있다.The self-dispersible pigments according to the invention can be used in numerous end-use applications. These applications include, but are not limited to, coatings, paints, paper, adhesives, latex, toners, fabrics, fibers, plastics and inks. Specific examples include, but are not limited to, printing inks for paper, textiles, fibers, metal decor and plastics, wood stains, recording equipment, and color filters. In particular, the self-dispersing pigments prepared by the process of the present invention are well suited for use in printing applications and wood stains. In one embodiment, inkjet inks incorporating the pigments of the present invention may be useful for high quality printing in inkjet photo printers.
본 발명의 한 측면은 상기 기재된 자가-분산성 안료를 사용하는 잉크젯 잉크 제제에 관한 것이다. 상기 안료를 함유하는 잉크젯 제제는 다음 중 하나 이상을 수행할 수 있다: 1) 인쇄 매체 상에서 고해상도 및 고밀도로 균일하고, 번짐없는 영상을 제공함; 2) 노즐 말단부에서의 잉크 건조로 인해 전형적으로 발생하는 노즐 막힘을 일으키지 않음; 3) 종이 상에서의 빠른 건조; 4) 양호한 광견뢰성 및 수견뢰성을 나타냄; 5) 양호한 장기간 보관 안정성을 나타냄; 6) 종이 질에 독립적인 인쇄 특성을 나타냄. One aspect of the invention relates to an inkjet ink formulation using the self-dispersible pigment described above. The inkjet formulation containing the pigment may perform one or more of the following: 1) provide a uniform, blur-free image at high resolution and density at high density on a print medium; 2) does not cause nozzle clogging, which typically occurs due to ink drying at the nozzle end; 3) rapid drying on paper; 4) good light fastness and water fastness; 5) good long term storage stability; 6) Independent printing characteristics of paper.
본 발명의 잉크 조성물은 상기 개질된 안료를 수성 비히클 및 임의의 적합한 첨가제와 조합하여 제조할 수 있다. 잉크 조성물 중 개질된 안료의 양 (중량비)은 약 0.1% 이상, 특히 약 10% 이상, 보다 구체적으로 약 20% 이상이다. 또한, 잉크 조성물 중 개질된 안료의 양 (중량비)은 약 12% 이하, 특히 약 8% 이하, 보다 구체적으로 약 5% 이하이다. 본 발명은 잉크 조성물 중 개질된 안료의 양 (중량비)이 약 2% 내지 약 12% 범위의 양으로 존재하는 실시양태를 포함한다.The ink composition of the present invention can be prepared by combining the modified pigment with an aqueous vehicle and any suitable additives. The amount (weight ratio) of the modified pigment in the ink composition is at least about 0.1%, especially at least about 10%, more particularly at least about 20%. In addition, the amount (weight ratio) of the modified pigment in the ink composition is about 12% or less, especially about 8% or less, more specifically about 5% or less. The present invention includes embodiments where the amount (weight ratio) of the modified pigment in the ink composition is present in an amount ranging from about 2% to about 12%.
수성 비히클은 물을 포함할 수 있거나, 또는 물과 함께 하나 이상의 수용성 유기 용매를 포함할 수 있다. 수용성 유기 용매는 물과 조합되어 수성 비히클을 형성할 수 있다. 수용성 유기 용매에는 알코올, 다가 알코올, 예컨대 에틸렌 글리콜, 케톤 및 케톤 알코올, 예컨대 아세톤 및 디아세톤 알코올, 에테르, 예컨대 테트라히드로푸란 및 디옥산, 다가 알코올의 저급 알킬 에테르, 예컨대 에틸렌 글리콜 모노메틸 (또는 모노에틸) 에테르, 질소-함유 용매, 예컨대 피롤리돈, N-메틸-2-피롤리돈, 황-함유 용매, 예컨대 티오디에탄올, 당 및 그의 유도체, 예컨대 글루코스, 글리세린의 옥시에틸렌 부가물 및 디글리세린의 옥시에틸렌 부가물이 포함될 수 있다. 수용성 유기 용매는 단독으로 또는 조합물로 사용될 수 있다. 물과 수용성 유기 용매의 혼합물이 사용되는 경우, 잉크 조성물 중 수용성 유기 용매의 양 (중량비)은 약 5% 이상, 특히 약 15% 이상, 보다 구체적으로 약 25% 이상이다. 또한, 잉크 조성물 중 수용성 유기 용매의 양 (중량비)은 약 50% 이하, 특히 약 30% 이하, 보다 구체적으로 약 15% 이하이다. 본 발명은 잉크 조성물 중 수용성 유기 용매의 양 (중량비)이 약 5% 내지 약 30%인 실시양태를 포함한다. 잉크 조성물 중 물의 양은 약 40% 이상, 특히 약 50% 이상, 보다 구체적으로 약 60% 이상이다. 또한, 잉크 조성물 중 물의 양 (중량비)은 약 90% 이하, 특히 약 80% 이하, 보다 구체적으로 약 70% 이하이다. 본 발명은 잉크 조성물 중 물의 양 (중량비)이 40% 내지 약 80%인 실시양태를 포함한다.The aqueous vehicle may comprise water, or it may comprise one or more water-soluble organic solvents with water. The water-soluble organic solvent may be combined with water to form an aqueous vehicle. Water-soluble organic solvents include alcohols, polyhydric alcohols such as ethylene glycol, ketones and ketone alcohols such as acetone and diacetone alcohols, ethers such as tetrahydrofuran and dioxane, lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl Sulfur-containing solvents such as thiodiethanol, sugars and derivatives thereof such as glucose, glycerin and oxyethylene adducts of glycerin, and di- An oxyethylene adduct of glycerin may be included. The water-soluble organic solvent may be used alone or in combination. When a mixture of water and a water-soluble organic solvent is used, the amount (weight ratio) of the water-soluble organic solvent in the ink composition is about 5% or more, particularly about 15% or more, and more specifically about 25% or more. The amount (weight ratio) of the water-soluble organic solvent in the ink composition is about 50% or less, particularly about 30% or less, more specifically about 15% or less. The present invention includes embodiments wherein the amount (weight ratio) of the water soluble organic solvent in the ink composition is from about 5% to about 30%. The amount of water in the ink composition is at least about 40%, especially at least about 50%, more particularly at least about 60%. In addition, the amount (weight ratio) of water in the ink composition is about 90% or less, especially about 80% or less, more specifically about 70% or less. The present invention includes embodiments wherein the amount (weight ratio) of water in the ink composition is from 40% to about 80%.
첨가제는 수많은 원하는 특성, 예컨대 특히 잉크젯 프린터의 요건에 잉크를 부합시키거나, 광 안정성, 스미어(smear) 내성, 점도, 표면 장력, 코팅 침투, 광학 밀도, 접착력, 하이라이터 내성 또는 크러스트(crust) 내성의 균형을 제공하는데 필요할 수 있는 특성을 부여하기 위해 수성 비히클에 도입될 수 있다. 침투제는, 예를 들면 번짐을 감소시키고, 인쇄 매체의 습윤을 향상시키고, 다르게는 인쇄 영상의 전체 성능을 향상시키기 위해 첨가될 수 있다. 침투제의 예에는 1 내지 4개의 탄소 원자를 갖는 알킬 알코올, 예컨대 에탄올, 글리콜 에테르, 예컨대 에틸렌 글리콜 모노메틸 에테르, 디올, 예컨대 1,2-알킬 디올, 포름아미드, 아세트아미드, 디메틸설폭사이드, 소르비톨 및 설폴란이 포함될 수 있으나, 이들로 한정되지는 않는다. 침투제는 단독으로 또는 조합물로 사용될 수 있다. 잉크 조성물 중 침투제의 양 (중량비)은 0% 내지 약 60%, 특히 약 2% 내지 약 40%, 보다 구체적으로 약 5% 내지 약 20% 범위이다. 본 발명은 잉크 조성물 중 침투제의 양 (중량비)이 약 10% 내지 약 15% 범위의 양으로 존재하는 실시양태를 포함한다.The additives can be used to meet a number of desired properties, such as the requirements of an ink jet printer, or to provide ink stability, light stability, smear resistance, viscosity, surface tension, coating penetration, optical density, adhesion, high lighter resistance or crust resistance ≪ / RTI > may be introduced into the aqueous vehicle to impart properties that may be needed to provide a balance of < RTI ID = 0.0 > Penetrating agents may be added, for example, to reduce bleed, improve wetting of the print media, or otherwise improve the overall performance of the printed image. Examples of penetrating agents include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, glycol ethers such as ethylene glycol monomethyl ether, diols such as 1,2-alkyldiols, formamides, acetamides, dimethylsulfoxide, sorbitol and But are not limited to, sulfolane. The penetrants may be used alone or in combination. The amount (weight ratio) of the penetrating agent in the ink composition ranges from 0% to about 60%, especially from about 2% to about 40%, more specifically from about 5% to about 20%. The present invention includes embodiments wherein the amount (weight ratio) of the penetrating agent in the ink composition is in the range of from about 10% to about 15%.
계면활성제는 잉크 조성물의 표면 장력을 감소시키기 위해 수성 매질에 첨가될 수 있다. 계면활성제는 음이온성 계면활성제, 비-이온성 계면활성제 및/또는 양이온성 계면활성제일 수 있다. 적합한 계면활성제에는 하기 기재된 것들, 및 미국 특허 제5,116,409호 (1992년 5월 26일에 특허 허여됨), 미국 특허 제5,861,447호 (1999년 1월 19일에 특허 허여됨) 및 미국 특허 제6,849,111호 (2005년 2월 1일에 특허 허여됨)에 기재된 것들이 포함될 수 있다 (이들은 각각 참고로 본원에 포함됨). The surfactant may be added to the aqueous medium to reduce the surface tension of the ink composition. The surfactant may be an anionic surfactant, a non-ionic surfactant, and / or a cationic surfactant. Suitable surfactants include those described below and those disclosed in U.S. Patent No. 5,116,409 (issued May 26, 1992), U.S. Patent No. 5,861,447 (issued January 19, 1999), and U.S. Patent No. 6,849,111 (Issued on February 1, 2005), each of which is incorporated herein by reference.
계면활성제는 널리 공지된 다양한 상표명, 예컨대 플루로닉(PLURONIC)® 시리즈 (뉴저지주 팔시파니 소재의 바스프 코포레이션(BASF Corporation)), 테트로닉(TETRONIC)® 시리즈 (뉴저지주 팔시파니 소재의 바스프 코포레이션), 알콰드(ARQUAD)® 시리즈 (일리노이주 시카고 소재의 아크조 케미컬 인크.(Akzo Chemical Inc.)), 트리톤(TRITON)® 시리즈 (코네티컷주 댄버리 소재의 유니온 카바이드 코포레이션(Union Carbide Corp.)), 서르포닉(SURFONIC)® 시리즈 (텍사스주 휴스턴 소재의 텍사코 케미칼 컴퍼니(Texaco Chemical Company)), 에토콰드(ETHOQUAD)® 시리즈 (일리노이주 시카고 소재의 아크조 케미칼 인크.), 아르민(ARMEEN)® 시리즈 (일리노이주 시카고 소재의 아크조 케미칼 인크.), 이코놀(ICONOL)® 시리즈 (뉴저지주 팔시파니 소재의 바스프 코포레이션), 서르피놀(SURFYNOL)® 시리즈 (팬실배니아주 앨런타운 소재의 에어 프로덕츠 앤드 케미칼즈, 인크.(Air Products and Chemicals, Inc.)) 및 에토민(ETHOMEEN)® 시리즈 (일리노이주 시카고 소재의 아크조 케미칼 인크.)하에 상업적으로 입수할 수 있다.Surfactants various trade names is well known, for example, Pluronic (PLURONIC) ® series (NJ, BASF Corporation, eight o'clock petticoat material (BASF Corporation)), Tetronic (TETRONIC) ® series (NJ, BASF Corporation, eight o'clock petticoat material) Al quad (ARQUAD) ® series (Akzo Chemical Inc., Chicago, Illinois. (Akzo Chemical Inc.)), Triton (TRITON) ® series (Union carbide Corporation (Union carbide Corp.) in Danbury, Conn material) standing reportage Nick (SURFONIC) ® series (Note Texaco Chemical Company of Houston, Texas (Texaco Chemical Company)), etoposide quad (ETHOQUAD) ® series (Akzo of Chicago material Chemical Inc.), Armin (ARMEEN) ® series (Akzo Chemicals Inc. of Chicago, Illinois), playing Ico (ICONOL) ® series (BASF Corporation, New Jersey, eight o'clock Trapani material), Management Interviews pinol (SURFYNOL) ® series (fan Banish Air Products and Chemicals of Allentown material's very, Inc.. (Air Products and Chemicals, Inc. )) and Etoile Min (ETHOMEEN) ® Series (available commercially under the Akzo Chemicals Inc.) in Chicago, Illinois have.
계면활성제는 단독으로 또는 조합물로 사용될 수 있다. 잉크 조성물 중 계면활성제의 양 (중량비)은 0% 내지 약 10%, 특히 약 0.1% 내지 약 10%, 보다 구체적으로 약 0.3% 내지 약 5% 범위일 수 있다. 본 발명은 잉크 조성물 중 계면활성제의 양 (중량비)이 약 0.1% 내지 약 8% 범위일 수 있는 실시양태가 포함된다.Surfactants may be used alone or in combination. The amount (weight ratio) of the surfactant in the ink composition may range from 0% to about 10%, especially from about 0.1% to about 10%, more specifically from about 0.3% to about 5%. The present invention includes embodiments in which the amount (weight ratio) of the surfactant in the ink composition can range from about 0.1% to about 8%.
하나 이상의 습윤제는 잠재 기간 동안 건조되어 일어날 수 있는 잉크젯 노즐의 막힘을 예방하기 위해 수성 비히클에 첨가될 수 있다. 습윤제는 높은 흡수성 및 수용해도를 갖는 물질로부터 선택될 수 있다. 습윤제의 예에는 폴리올 예컨대 글리세롤, 락탐, 예컨대 2-피롤리돈, 우레아 화합물, 예컨대 우레아, 1,3-디메틸이미다졸리디논, 사카라이드, 예컨대 소르비톨, 1,4-시클로헥산디메타놀, 1-메틸-2-피페리돈, N-에틸아세트아미드, 3-아미노-1,2-프로판디올, 에틸렌 카르보네이트; 부티롤아세톤 및 리포닉(Liponic) EG-1이 포함되나, 이들로 한정되지는 않는다. 습윤제의 사용량에는 특정 제한이 없으나, 일반적으로 잉크 조성물 중 습윤제의 양 (중량비)은 0% 내지 약 30%, 특히 약 1% 내지 약 15%, 보다 구체적으로 약 5% 내지 약 10% 범위일 수 있다.One or more wetting agents may be added to the aqueous vehicle to prevent clogging of the inkjet nozzles that may occur during latent periods of drying. The wetting agent can be selected from materials having high water absorption and water solubility. Examples of wetting agents include polyols such as glycerol, lactam such as 2-pyrrolidone, urea compounds such as urea, 1,3-dimethylimidazolidinone, saccharides such as sorbitol, 1,4-cyclohexanedimethanol, 1- Methyl-2-piperidone, N-ethylacetamide, 3-amino-1,2-propanediol, ethylene carbonate; Butyryl acetone, and Liponic EG-1. The amount of the wetting agent to be used is not particularly limited, but the amount (weight ratio) of the wetting agent in the ink composition may generally be in the range of 0% to about 30%, particularly about 1% to about 15%, more specifically about 5% have.
중합체는 인쇄 매체 상에서 영상의 물-견뢰성, 마찰 및 하이라이터 견뢰성을 향상시키기 위해 잉크 조성물에 첨가될 수 있다. 적합한 중합체에는 폴리비닐 알코올, 폴리에스테르, 폴리에스테르멜라민, 스티렌-아크릴산 공중합체, 스티렌-말레산 공중합체, 스티렌-말레산-알킬 아크릴레이트 공중합체, 스티렌-메타크릴산 공중합체, 스티렌-메타크릴산-알킬 아크릴레이트 공중합체, 스티렌-말레산 하트 에스테르 공중합체, 비닐-나프탈렌-아크릴산 공중합체, 비닐 나프탈렌-말레산 공중합체 및 이들의 염이 포함될 수 있으나, 이들로 한정되지는 않는다. 잉크 조성물 중 중합체의 양 (중량비)은 0% 내지 약 5%, 특히 약 0.1% 내지 약 3%, 보다 구체적으로 약 0.2% 내지 약 2.5% 범위일 수 있다. 본 발명은 잉크 조성물 중 중합체의 양 (중량비)가 약 0.1% 내지 약 3.0% 범위일 수 있는 실시양태를 포함한다.The polymer may be added to the ink composition to improve the water-fastness, friction and high lighter fastness of the image on the print medium. Suitable polymers include, but are not limited to, polyvinyl alcohols, polyesters, polyester melamines, styrene-acrylic acid copolymers, styrene-maleic acid copolymers, styrene-maleic-alkyl acrylate copolymers, styrene-methacrylic acid copolymers, But are not limited to, acid-alkyl acrylate copolymers, styrene-maleic acid hard ester copolymers, vinyl-naphthalene-acrylic acid copolymers, vinyl naphthalene-maleic acid copolymers and salts thereof. The amount (weight ratio) of the polymer in the ink composition may range from 0% to about 5%, especially from about 0.1% to about 3%, more specifically from about 0.2% to about 2.5%. The present invention includes embodiments wherein the amount (weight ratio) of the polymer in the ink composition may range from about 0.1% to about 3.0%.
본 발명의 잉크 조성물은 다양한 pH 조정제를 사용하여 원하는 pH로 완충될 수 있다. 적합한 pH 조정제에는 알칼리 히드록시드, 알칼리 카르보네이트 및 바이카르보네이트, 트리에틸아민, 디메틸에탄올아민, 트리에탄올아민, 미네랄 산, 염산 및 황산이 포함될 수 있다. pH 조정제는 단독으로 또는 조합물로 사용될 수 있다. 잉크 조성물 중 pH 조정제의 양 (중량비)은 0% 내지 약 3.0%, 특히 약 0.1% 내지 약 2.0%, 보다 구체적으로 약 0.5% 내지 약 1.5% 범위일 수 있다. 본 발명은 잉크 조성물 중 pH 조정제의 양 (중량비)이 약 0.2% 내지 약 2.5% 범위인 실시양태를 포함한다.The ink composition of the present invention can be buffered to a desired pH using various pH adjusting agents. Suitable pH adjusting agents may include alkali hydroxides, alkaline carbonates and bicarbonates, triethylamine, dimethylethanolamine, triethanolamine, mineral acids, hydrochloric acid and sulfuric acid. The pH adjusting agent may be used alone or in combination. The amount (weight ratio) of the pH adjusting agent in the ink composition may range from 0% to about 3.0%, especially from about 0.1% to about 2.0%, more specifically from about 0.5% to about 1.5%. The present invention includes embodiments wherein the amount (weight ratio) of the pH adjusting agent in the ink composition ranges from about 0.2% to about 2.5%.
또한, 보존제, 예컨대 살생제 및 살진균제가 잉크 조성물에 첨가될 수 있다. 적합한 보존제의 예에는 나트륨 벤조에이트, 펜타클로로페놀 나트륨, 2-피리딘티올-1-옥사이드 나트륨, 나트륨 소르베이트, 나트륨 데히드로아세테이트, 벤즈이소티아졸리논, 1,2-디벤조티아졸린-3-온, 메틸이소티아졸리논 및 클로로메틸이소티아졸리논이 포함된다. 상업적으로 입수가능한 살생제에는 우카르시드(UCARCIDE)® 250 (유니온 카바이드 컴퍼니로부터 입수가능함), 프록셀® CRL, 프록셀® BDN, 프록셀® GXL, 프록셀® XL-2, 프록셀® TN (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함), 다우이시즈(Dowicides)® (미시간주 미들랜드 소재의 다우 케미칼(Dow Chemical)), 뉴오셉트(Nuosept)® (뉴저지주 피스키타웨이 소재의 휠스 아메리카, 인크.(Huls America, Inc.)), 오미딘즈(Omidines)® (코네티컷주 체셔 소재의 올린 코포레이션(Olin Corp.)), 노프코시즈(Nopcocides)® (팬실배니아주 앰블러 소재의 헨켈 코포레이션(Henkel Corp.)), 트로이산스(Troysans)® (뉴저지주 뉴어크 소재의 트로이 케미칼 코포레이션(Troy Chemical Corp.)) 및 엑스빙스® (오하이오주 신시내티 소재의 PMC 스페셜티즈 그룹, 인크.)가 포함된다. 보존제는 단독으로 또는 조합물로 사용될 수 있다. 잉크 조성물 중 보존제의 양 (중량비)은 0% 내지 약 1.5%, 특히 약 0.05% 내지 약 1.0%, 보다 구체적으로 약 0.1% 내지 약 0.3% 범위일 수 있다. 본 발명은 잉크 조성물 중 보존제의 양 (중량비)이 약 0.05% 내지 약 0.5% 범위일 수 있는 실시양태를 포함한다.Preservatives, such as biocides and fungicides, may also be added to the ink composition. Examples of suitable preservatives include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazoline- Methyl isothiazolinone, and chloromethyl isothiazolinone. Commercially available biocides include Wu carboxylic seed (UCARCIDE) ® 250 (available from Union Carbide Company, are possible), Proxel ® CRL, Proxel ® BDN, Proxel ® GXL, Proxel ® XL-2, Proxel ® TN (available from Arch Chemical's of Georgia Smyrna material available), dawooyi Siege (Dowicides) ® (MI Dow Chemical Company of Midland (Dow Chemical)), nyuoh septeu (Nuosept) ® (NJ piece Kita way hwilseu material Americas , Inc.. (Huls America, Inc.)) , Omi dinjeu (Omidines) ® (De Corporation of Cheshire, Conn material (Olin Corp.)), Nopco Siege (Nopcocides) ® (Henkel paensil Vanity very Ambler material Corporation (Henkel Corp.)), Troy Sans (Troysans) ® (Troy Chemical Corp. of Newark, NJ material (Troy Chemical Corp.)) and X Savings establishments ® (Ohio, including the PMC Special Tees group, Inc. of Cincinnati,) do. Preservatives may be used alone or in combination. The amount (by weight) of preservative in the ink composition may range from 0% to about 1.5%, especially from about 0.05% to about 1.0%, more specifically from about 0.1% to about 0.3%. The present invention includes embodiments wherein the amount (weight ratio) of the preservative in the ink composition may range from about 0.05% to about 0.5%.
잉크 조성물은 하나 이상의 점도 조정제를 함유할 수 있다. 점도 조정제에는 로진 화합물, 알긴산 화합물, 폴리비닐 알코올, 히드록시프로필 셀룰로스, 카르복시메틸 셀룰로스, 히드록시에틸 셀룰로스, 메틸 셀룰로스, 폴리아크릴산의 염, 폴리비닐 피롤리돈, 아라비아 고무 및 전분이 포함될 수 있다. 잉크 조성물 중 점도 조정제의 양 (중량비)은 0% 내지 약 10%, 특히 약 0.5% 내지 약 8%, 보다 구체적으로 약 1% 내지 약 5% 범위일 수 있다. 본 발명은 잉크 조성물 중 점도 조정제의 양 (중량비)이 약 1% 내지 약 7% 범위일 수 있는 실시양태를 포함한다.The ink composition may contain one or more viscosity modifiers. The viscosity adjusting agent may include a rosin compound, an alginic acid compound, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, salts of polyacrylic acid, polyvinyl pyrrolidone, gum arabic and starch. The amount (weight ratio) of the viscosity modifier in the ink composition may range from 0% to about 10%, especially from about 0.5% to about 8%, more specifically from about 1% to about 5%. The present invention includes embodiments wherein the amount (weight ratio) of the viscosity modifier in the ink composition may range from about 1% to about 7%.
또한, 수성 비히클에 도입될 수 있는 다른 첨가제에는 항산화제, 자외선 흡수제, 킬레이트화제, 전기 전도율 조절제, 점도 조정제, 산소 흡수제, 항-코게이션(kogation)제, 항-컬링(curling)제, 항번짐제, 소포제 및 완충제가 포함될 수 있다. 본 발명의 잉크 조성물은 본 발명의 안료 분산액 이외에 하나 이상의 착색제 또한 함유할 수 있다.Other additives that may be introduced into the aqueous vehicle also include antioxidants, ultraviolet absorbers, chelating agents, electrical conductivity modifiers, viscosity modifiers, oxygen sorbents, kogation agents, anti-curling agents, Anti-foaming agents, and buffering agents. The ink composition of the present invention may also contain at least one coloring agent in addition to the pigment dispersion of the present invention.
본 발명의 잉크 조성물은 특히 잉크 조성물의 액적이 인쇄 장비로부터 분출되고 기재에 침착되어 영상을 생성하는 잉크젯 인쇄용 잉크 조성물로서 사용하기에 적합하다. 적합한 인쇄 장비에는 연속식 잉크 젯(Continuous Ink Jet; CIJ), 드롭-온-디맨드(Drop-on-Demand) 밸브 (DoD 밸브), 드롭-온-디맨드 피에조-일렉트릭(Piezo-Electric) (DoD 피에조) 및 열적 잉크 젯(Thermal Ink Jet; TIJ)이 포함되나, 이들로 한정되지는 않는다. 유사하게, 보통지, 본드지, 코팅지, 투명재, 직물, 플라스틱, 중합체 필름 및 무기 기재를 비롯한 임의의 적합한 기재를 사용할 수 있다. 그러나, 당업자는 상기 잉크 조성물이 또한 일반 기록 기구 적용 및 스탬프 적용 (이들로 한정되지는 않음)을 비롯한 다른 적용에도 사용될 수 있다는 것을 인지해야 한다. The ink composition of the present invention is particularly suitable for use as an ink composition for inkjet printing in which a droplet of the ink composition is ejected from the printing equipment and deposited on the substrate to produce an image. Suitable printing equipment includes continuous ink jet (CIJ), drop-on-demand valves (DoD valves), drop-on-demand piezo-electric (DoD piezo And Thermal Ink Jet (TIJ). ≪ / RTI > Similarly, any suitable substrate can be used including plain paper, bond paper, coated paper, transparencies, fabrics, plastics, polymer films and inorganic substrates. However, those skilled in the art should appreciate that the ink composition may also be used in other applications including, but not limited to, conventional recorder application and stamp application.
본 발명의 잉크 조성물은 단독으로 사용되거나, 컬러 언더레이(color underlay)와 함께 사용되어 블랙 영상을 생성하거나, 또는 다른 잉크 조성물과 함께 사용되어 컬러 영상을 생성할 수 있다. 몇몇 실시양태에서, 본 발명의 잉크 조성물은 다른 잉크 조성물(들), 예컨대 시안(cyan) 잉크, 마젠타(magenta) 잉크 및/또는 황색 잉크와 함께 사용된다. 다른 실시양태에서, 시안 잉크, 마젠타 잉크 및 황색 잉크는 과도인쇄(overprint)되어 블랙 영상을 형성하고, 상기 인쇄는 본 발명의 블랙 잉크의 인쇄와 함께 사용된다. The ink composition of the present invention may be used alone or in combination with a color underlay to produce a black image, or may be used with other ink compositions to produce a color image. In some embodiments, the ink composition of the present invention is used with other ink composition (s) such as cyan ink, magenta ink and / or yellow ink. In another embodiment, the cyan ink, the magenta ink, and the yellow ink are overprinted to form a black image, which is used in conjunction with the printing of the black ink of the present invention.
우드 스테인Wood stain
본 발명의 또다른 측면은 우드 스테인 및 코팅으로서 상기 기재된 자가-분산성 안료를 사용하는 수성 제제에 관한 것이다. 상기 안료를 함유하는 우드 스테인 제제는 하기 특성 중 하나 이상을 나타낼 수 있다: 1) 양호한 우드 흡수성 및 접착력; 2) 양호한 투명도; 및 3) 탁월한 물 및 광 내성. Another aspect of the invention relates to aqueous formulations using the self-dispersing pigments described above as wood stains and coatings. Wood stain formulations containing such pigments may exhibit one or more of the following properties: 1) Good wood absorbency and adhesion; 2) Good transparency; And 3) excellent water and light resistance.
물 내성은 침지 영역 대 대조군의 우드 스테인의 측정된 DE* 값의 차로써 측정한다. 낮은 DE* 값은 높은 물 내성을 나타낼 수 있다. DE*이 작은 경우, 이는 분해 또는 손실로 인한 색상 변화가 최소 내지 없음을 의미할 수 있다. 예를 들면, 낮은 DE* 값은 카르복시 개질된 안료 분산액에서 나타난 바와 같이 높은 물 내성을 나타낼 수 있다. 개질된 안료 분산액의 DE* 값은 약 0 내지 약 3일 수 있다. 한 특정 실시예는 4-아미노벤조산으로 개질된 안료이다. 또다른 실시예에서, 카르복시 개질된 청색 안료 15 및 황색 안료 74 분산액은 각각 약 0.19 및 0.43의 낮은 DE* 값을 가졌다. 델타 E는 두 색상 사이의 차이이다. L, a, 및 b 값은 구형 색상(spherical color)에 기초한 측정값이다. +L=백색, -L=흑색, +a=적색, -a=녹색, +b=황색, -b=청색. C는 색도 (채도)이고, H는 색깔이다. 판독은 분광광도계를 이용하여 측정한다. The water resistance is determined by the difference in the measured DE * value of the wood stain of the control versus the control area. Low DE * values can indicate high water resistance. If DE * is small, it may mean that there is minimal or no color change due to decomposition or loss. For example, a low DE * value can indicate a high water resistance as shown in a carboxy modified pigment dispersion. The DE * value of the modified pigment dispersion may be from about 0 to about 3. One particular example is a pigment modified with 4-aminobenzoic acid. In another embodiment, the carboxy modified
코팅coating
상기 안료를 함유하는 코팅 제제는 하기 특성 중 하나 이상을 나타낼 수 있다: 1) 기재, 예컨대 금속, 종이, 유리, 플라스틱 및 우드에 대한 양호한 접착력; 2) 적용 및 건조의 용이성; 3) 양호한 날씨 견뢰성, 물 및 광 내성; 4) 양호한 광택 유지력; 및 5) 양호한 화학물질 내성 및 응집 내성. Coating formulations containing such pigments can exhibit one or more of the following properties: 1) Good adhesion to substrates, such as metals, paper, glass, plastic and wood; 2) ease of application and drying; 3) Good weather fastness, water and light resistance; 4) Good gloss retention; And 5) good chemical resistance and flocculation resistance.
물 내성과 마찬가지로, 코팅의 강산 및 강염기에 대한 내성은 스포팅된 영역 대 대조군의 DE* 값의 차로써 측정한다. 개질된 안료 분산액의 DE* 값은 약 0 내지 약 3일 수 있다. 한 실시예에서, 개질된 카본 블랙을 함유하는 코팅은 산 내성에 대해 약 0.08의 낮은 DE* 값을 가졌다. 또다른 실시예에서, 개질된 청색 안료 15번을 함유하는 코팅은 강염기에 대한 내성에 대해 약 1.56의 낮은 DE* 값을 가졌다. As with water tolerance, the resistance of the coating to strong acids and strong bases is measured by the difference in the DE * value of the spotted area versus the control. The DE * value of the modified pigment dispersion may be from about 0 to about 3. In one embodiment, the coating containing the modified carbon black had a low DE * value of about 0.08 against acid tolerance. In another embodiment, the coating containing modified
컬러 필터Color filter
본 발명의 또다른 측면은 컬러 필터에 상기 기재된 자가-분산성 안료를 사용하는 수성 제제에 관한 것이다. 컬러 필터의 적용은 데스크탑 모니터/랩탑 스크린, LCD TV 스크린, 휴대폰 디스플레이 패널, 디지털 카메라 스크린 및 GPS 패널을 비롯한 (이에 한정되지는 않음) 디스플레이 영상 분야에서 발견된다. 본 발명의 안료를 함유하는 컬러 필터 제제는 하기 특성 중 하나 이상을 나타낼 수 있다: 1) 유리 및 플라스틱 필름 기재에의 양호한 접착력; 2) 양호한 투명도; 3) 적용 및 건조의 용이성; 및 4) 양호한 열 및 광 내성. Another aspect of the invention is an aqueous formulation using the self-dispersible pigment described above in a color filter. The application of color filters is found in the field of display imaging, including, but not limited to, desktop monitor / laptop screens, LCD TV screens, mobile phone display panels, digital camera screens and GPS panels. Color filter formulations containing the pigments of the present invention may exhibit one or more of the following properties: 1) Good adhesion to glass and plastic film substrates; 2) Good transparency; 3) ease of application and drying; And 4) good heat and light resistance.
특정 컬러 필터의 투과 값을 측정하여 그의 유용성을 결정한다. 컬러 필터는 좁은 밴드에서 최대 투과율을 가져 최대 효용성을 제공할 수 있다. The transmissivity of a particular color filter is measured to determine its usefulness. Color filters have maximum transmittance in a narrow band and can provide maximum efficacy.
한 실시양태에서, 카본 블랙은 투과 밴드를 갖지 않을 수 있고, 마그네타 안료 분산액은 약 520 내지 약 560 nm 범위의 가장 낮은 투과를 가질 수 있고, 황색 안료 분산액은 약 400 내지 약 480 nm 범위의 가장 낮은 투과를 가질 수 있고, 시안 안료 분산액은 약 600 내지 약 680 nm 범위의 가장 낮은 투과를 가질 수 있다. In one embodiment, the carbon black may not have a transmission band, the magnet pigment dispersion may have the lowest transmission in the range of about 520 to about 560 nm, and the yellow pigment dispersion may have an impurity in the range of about 400 to about 480 nm And the cyan pigment dispersion may have the lowest transmission in the range of about 600 to about 680 nm.
직물 인쇄Textile printing
본 발명의 또다른 측면은 직물 인쇄 적용에 상기 기재한 자가-분산성 안료를 사용하는 수성 제제에 관한 것이다. 본 발명의 안료를 함유하는 직물 인쇄 제제는 하기 특성 중 하나 이상을 나타낼 수 있다: 1) 직물, 예컨대 면직물, 나일론, 폴리에스테르, 모직물, 폴리아크릴계, 또는 이들의 혼방에의 양호한 접착력; 2) 적용 및 건조의 용이성; 3) 양호한 물 및 광 내성; 및 4) 양호한 세탁견뢰성. Another aspect of the invention is an aqueous formulation using the self-dispersible pigment described above in fabric printing applications. The textile printing formulations containing the pigments of the present invention may exhibit one or more of the following properties: 1) Good adhesion to fabrics such as cotton fabrics, nylons, polyester, wool, polyacrylic, or blends thereof; 2) ease of application and drying; 3) good water and light resistance; And 4) good wash fastness.
착색된 직물의 세탁견뢰성 및 수견뢰성 특성은 대조군 대 세탁된 직물의 DE* 값의 차로써 측정할 수 있다. The fastness to washing and water fastness properties of the colored fabrics can be measured by the difference of the DE * value of the fabric versus the washed fabric.
개질된 안료 분산액의 DE* 값은 약 0 내지 약 3일 수 있다. 한 실시예에서, 개질된 카본 블랙은 약 0.23의 낮은 DE* 값을 가질 수 있다. 또다른 실시예에서, 개질된 황색 안료 74번은 약 6.72의 높은 DE* 값을 가질 수 있다.The DE * value of the modified pigment dispersion may be from about 0 to about 3. In one embodiment, the modified carbon black may have a low DE * value of about 0.23. In another embodiment, the modified
실시예Example
본 발명의 예시적인 실시양태를 하기 실시예에 제공한다. 하기 실시예는 본 발명을 예시하고 본 발명을 수행 및 사용함에 있어 당업자를 돕기 위해 제시된다. 실시예는 본 발명의 범위를 어떠한 방식으로든 다르게 제한하는 것으로 의도되지 않는다.Exemplary embodiments of the invention are provided in the following examples. The following examples are presented to illustrate the invention and to aid those skilled in the art in making and using the invention. The embodiments are not intended to otherwise limit the scope of the invention in any way.
실시예 1Example 1
안료 분산액 (클로로설폰산 및 티오닐 클로라이드에서의 클로로설폰화 후 소분자 부착의 실시예).Pigment dispersion (an example of small molecule attachment after chlorosulfonation in chlorosulfonic acid and thionyl chloride).
1차 입도가 20 nm이고 B.E.T 표면적이 160 m2/g인, 데구사 (일리노이주 버르 릿지)에서 시판하는 기체 카본 블랙 (65 g)을 332 g의 실험실 등급 클로로설폰산과 120-4℃에서 20시간 동안 클로로설폰화하였다. 반응 혼합물을 56℃로 냉각시키고, 68.5 g의 티오닐 클로라이드를 적가 도입하였다. 모든 티오닐 클로라이드를 첨가한 후, 반응 덩어리를 103-5℃로 다시 가열하고, 상기 온도에서 4시간 동안 유지하였다. 이어서, 반응 혼합물을 실온으로 냉각시키고, 켄칭 온도를 -5℃ 미만으로 제어하면서 물 및 얼음으로 켄칭하였다. 침전된 생성물을 여과에 의해 단리하고, 용해된 물질이 없도록 빙냉수 (<5℃)로 세척하였다. 이어서, 생성물 케이크 (253 g)를 2-5℃에서 15.5 g 진한 염산 (37%)을 함유하는 140 g 탈이온수 중 에틸 4-아미노벤조에이트 (알드리치(Aldrich)사의 실험실 등급, 21.7 g)의 용액과 반응시켰다. 2000 rpm에서 30분 동안 혼합한 후, 이를 5000 rpm에서 0.4 mm YTZ 미디어 (일리노이주 크리스탈 레이크 소재의 쿼켄부시 캄파니, 인크.(Quackenbush Co., Inc.)로부터 입수가능함)를 사용하여 혹크마이어(Hockmeyer) 미디어 밀 (노쓰 캘리포니아주 엘리자베쓰 시티 소재의 혹크마이어 이큅먼트 코퍼레이션(Hockmeyer Equipment Corp.)으로부터 입수가능함)에서 밀링시켜 온도를 10℃로 상승시키고, 20% 나트륨 아세테이트 용액의 첨가로 pH를 4.7로 상승시켰다. 밀링을 다시 5시간 동안 지속하였다. 밀링한 지 1시간 후, 칼슘 비함유 수산화나트륨 (23 g)의 첨가로 pH를 12.6으로 상승시켰다. 반응 혼합물을 밀에서 꺼내고, 85℃로 2시간 동안 가열하여 메틸 에스테르를 가수분해하였다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 18% 고체로 농축시키고, (0.3%, wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물을 0.7 ㎛ GF 필터를 통해 여과하였다.Gaseous carbon black (65 g), commercially available from Degussa (Burrridge, IL), having a primary particle size of 20 nm and a BET surface area of 160 m 2 / g, was mixed with 332 g of lab grade chlorosulfonic acid Lt; / RTI > The reaction mixture was cooled to 56 [deg.] C and 68.5 g of thionyl chloride was added dropwise. After all of the thionyl chloride was added, the reaction mass was heated again to 103-5 캜 and held at that temperature for 4 hours. The reaction mixture was then cooled to room temperature and quenched with water and ice while controlling the quenching temperature to below -5 < 0 > C. The precipitated product was isolated by filtration and washed with ice cold water (<5 ° C) to free the dissolved material. The product cake (253 g) was then added to a solution of ethyl 4-aminobenzoate (laboratory grade, Aldrich, 21.7 g) in 140 g deionized water containing 15.5 g concentrated hydrochloric acid (37% ≪ / RTI > After mixing for 30 minutes at 2000 rpm, it was mixed with 0.4 mm YTZ media (available from Quackenbush Co., Inc., Crystal Lake, Ill.) At 5000 rpm, Hockmeyer media mill (available from Hockmeyer Equipment Corp., Elizabeth City, Calif.) To raise the temperature to 10 ° C and to pH 4.7 with the addition of 20% sodium acetate solution . The milling was continued for another 5 hours. One hour after the milling, the pH was raised to 12.6 by the addition of calcium-free sodium hydroxide (23 g). The reaction mixture was removed from the mill and heated to 85 [deg.] C for 2 hours to hydrolyze the methyl ester. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 18% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Smyrna, GA). Finally, the product was filtered through a 0.7 탆 GF filter.
실시예 2-9Examples 2-9
실시예 2-9는 상기 실시예 1에 대해 기재한 것과 동일한 방법에 따라 제조하였다. Example 2-9 was prepared according to the same method as described for Example 1 above.
1 데구사 (일리노이주 버 릿지) 1 Degussa (Burridge, Illinois)
2 시바 (CIBA; 델라웨어주 뉴포트)사의 PB15:4 2 PB15: 4 from CIBA (Newport, Del.)
3 바스프 (뉴저지주 마운트 올리브)사의 PB 15:3, 큰 입자는 0.7 ㎛ TCLP로 여과하기 전 5분 동안 10,000 rpm에서 원심분리로 분리하였다. 3 PB 15: 3 from BASF (Mount Olive, NJ), and the larger particles were separated by centrifugation at 10,000 rpm for 5 minutes before filtration with 0.7 μm TCLP.
4 클라리언트 컬러즈(Clariant Colors; 노쓰캐롤라이나주 샬롯)사의 PB15:3 4 PB15: 3 from Clariant Colors (Charlotte, North Carolina)
[표 1 계속] [Table 1 Continued]
실시예 전반에서, 간결함을 위하여 약어를 사용하였다. "H"는 시간을 나타내고, "AP"는 아미노페놀을 나타내고, "SA"는 설파닐산을 나타내고, "4ABA"는 4-아미노벤조산을 나타낸다. In the first half of the Examples, abbreviations were used for brevity. "H" represents time, "AP" represents aminophenol, "SA" represents sulfanilic acid, and "4ABA" represents 4-aminobenzoic acid.
실시예 10Example 10
안료 분산액 (부착을 통한 상이한 염 형태 형성의 실시예 - 예를 들어 테트라메틸 암모늄 염).Pigment dispersion (an example of the formation of different salt forms via attachment - for example, tetramethylammonium salts).
1차 입도가 20 nm이고 B.E.T 표면적이 160 m2/g인, 데구사에서 시판하는 기체 카본 블랙 (66 g)을 348 g의 실험실 등급 클로로설폰산과 122-7℃에서 19시간 동안 클로로설폰화하였다. 반응 혼합물을 74℃로 냉각시키고, 30.0 g의 티오닐 클로라이드를 적가 도입하였다. 모든 티오닐 클로라이드를 첨가한 후, 반응 덩어리를 134℃로 다시 가열하고, 상기 온도에서 1시간 동안 유지하였다. 이어서, 반응 혼합물을 실온으로 냉각시키고, 켄칭 온도를 -5℃ 미만으로 제어하면서 물 및 얼음으로 켄칭하였다. 침전된 생성물을 여과에 의해 단리하고, 용해된 물질이 없도록 빙냉수 (<5℃)로 세척하였다. 이어서, 생성물 케이크 (326 g)를 빙냉된 탈이온수에서 혼합하여 pH=1.5인 슬러리를 얻었다. 초기에 테트라메틸 수산화암모늄 용액 (25%)으로 pH를 4.5로 상승시켰다. 25℃에서 40.3 g 테트라메틸 수산화암모늄 용액 (25%) 및 8 g의 서르피놀 CT-141 (팬실배니아주 앨런타운 소재의 에어 프로덕츠 앤드 케미칼즈, 인크.로부터 입수가능함)을 함유하는 90 g 탈이온수 중 4-아미노벤조산 (알드리치사의 실험실 등급, 18 g)의 용액으로 pH를 추가로 6.5로 상승시켰다. 이어서, 이를 추가의 테트라메틸 수산화암모늄 용액 (25%)과 9.6의 최종 pH로 잠시 혼합하였다. 혼합물을 4℃로 냉각시킨 후, 4800 rpm에서 0.4 mm YTZ 미디어 (일리노이주 크리스탈 레이크 소재의 쿼켄부시 캄파니, 인크.로부터 입수가능함)를 사용하여 혹크마이어 미디어 밀 (노쓰 캘리포니아주 엘리자베쓰 시티 소재의 혹크마이어 이큅먼트 코퍼레이션으로부터 입수가능함)에서 밀링시켜 온도를 37℃로 상승시키고, 테트라메틸 수산화암모늄 용액의 첨가로 pH를 8.8 초과로 제어하였다. 밀링을 총 4시간 동안 지속하였다. 반응 혼합물을 밀에서 꺼내고, 60-76℃로 15시간 동안 가열하였다. 추가의 테트라메틸 수산화암모늄을 첨가하여 pH를 9.2로 상승시켰다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 17% 고체로 농축시키고, (0.3%, wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물의 일부 (112 g)를 0.7 ㎛ GF 필터를 통해 여과하였다.Gaseous carbon black (66 g) commercially available from Degussa, with a primary particle size of 20 nm and a BET surface area of 160 m 2 / g, was chlorosulfonized with 348 g of laboratory grade chlorosulfonic acid at 122-7 ° C for 19 hours . The reaction mixture was cooled to 74 DEG C and 30.0 g of thionyl chloride was added dropwise. After all the thionyl chloride was added, the reaction mass was heated again to 134 ° C and held at this temperature for 1 hour. The reaction mixture was then cooled to room temperature and quenched with water and ice while controlling the quenching temperature to below -5 < 0 > C. The precipitated product was isolated by filtration and washed with ice cold water (<5 ° C) to free the dissolved material. The product cake (326 g) was then mixed in ice-cold deionized water to obtain a slurry having pH = 1.5. The pH was initially raised to 4.5 with tetramethyl ammonium hydroxide solution (25%). 90 g deionized water containing 25.0 g of tetramethylammonium hydroxide solution (25%) and 40 g of Surfinol CT-141 (available from Air Products and Chemicals, Inc., Allentown, Pancylone, The pH was further raised to 6.5 with a solution of 4-aminobenzoic acid (laboratory grade, Aldrich, 18 g). This was then mixed briefly with additional tetramethyl ammonium hydroxide solution (25%) and a final pH of 9.6. The mixture was cooled to 4 DEG C and then pelletized using a 0.4 mm YTZ media at 4800 rpm (available from Quark & Co., Inc., Crystal Lake, Ill.) In a Brookhaven media mill Available from Meyer Equipment Corporation) to raise the temperature to 37 DEG C and to control the pH to greater than 8.8 by addition of the tetramethyl ammonium hydroxide solution. The milling was continued for a total of 4 hours. The reaction mixture was removed from the mill and heated to 60-76 [deg.] C for 15 hours. Additional tetramethyl ammonium hydroxide was added to raise the pH to 9.2. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 17% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, a portion of the product (112 g) was filtered through a 0.7 탆 GF filter.
실시예 11Example 11
안료 분산액 (클로로설폰산 중 PB15의 클로로설폰화; 설파닐산과의 부착 및 PB15 분산의 실시예).Pigment dispersion (chlorosulfonation of PB15 in chlorosulfonic acid; attachment with sulfanilic acid and examples of PB15 dispersion).
뉴케믹 (Newchemic; 뉴저지주 몬트베일)에서 시판하는 청색 안료 15:1번 (60 g)을 320 g의 실험실 등급 클로로설폰산과 110-118℃에서 1시간 동안 클로로설폰화하였다. 반응 혼합물을 25℃로 냉각시키고, 켄칭 온도를 0℃ 미만으로 제어하면서 물 및 얼음에서 켄칭하였다. 침전된 생성물을 여과에 의해 단리하고, 용해된 물질이 없도록 pH <4에서 빙냉수 (<5℃)로 세척하였다. 이어서, 생성물 케이크 (365 g)를 잘 혼합하면서 (1100 rpm) 탈이온수 (200 g) 중 설파닐산 (20 g, 사우스 캐롤라이나주 포트 밀 소재의 내이션 포드 케미칼(Nation Ford Chemical)로부터 입수가능함), Ca 비함유 수산화나트륨 과립 (6.4 g) 및 중탄산나트륨 (21.7 g)의 용액에 첨가하였다. pH를 추가의 37 g 중탄산나트륨 및 21 g 탄산나트륨으로 8.0 초과로 제어하였다. 이어서, 혼합물을 4000 rpm에서 0.2 mm YTZ 미디어 (일리노이주 크리스탈 레이크 소재의 쿼켄부시 캄파니, 인크.로부터 입수가능함)를 사용하여 혹크마이어 미디어 밀 (노쓰 캘리포니아주 엘리자베쓰 시티 소재의 혹크마이어 이큅먼트 코퍼레이션으로부터 입수가능함)에서 밀링하였다. 온도를 80℃로 상승시키고, 혼합물을 3시간 동안 밀링하였다. 반응 혼합물을 밀에서 꺼내고, 83℃로 가열하였다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 약 5% 고체로 농축시켜 1446 g의 액체를 얻었다. 액체 생성물의 일부 (220 g)를 사용하여 클래리언트 컬러즈 (노쓰캐롤라이나주 샬롯)사의 청색 안료 15:3의 40 g을 분산시키고, 7000 rpm에서 3시간 동안 밀링하였다. 칼슘 비함유 수산화나트륨 용액 (1.4 g, 25%)의 적가로 pH를 8 초과로 지속적으로 조정하였다. 생성물을 밀에서 꺼내고, 86℃로 가열하고, 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 다시 한번 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 약 12% 고체로 농축시키고, (0.3%, wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 보다 큰 입자를 3,200 rpm에서 15분 동안 원심분리로 제거하고, 생성물 (210 g)을 0.7 ㎛ GF 필터를 통해 여과하였다.Blue pigment 15: 1 (60 g), commercially available from Newchemic (Montville, NJ), was chlorosulfonized with 320 g of lab grade chlorosulfonic acid at 110-118 ° C for 1 hour. The reaction mixture was cooled to 25 캜 and quenched in water and ice while controlling the quenching temperature to below 0 캜. The precipitated product was isolated by filtration and washed with ice cold water (<5 ° C) at pH <4 to free the dissolved material. Subsequently, sulfanilic acid (20 g, available from Nation Ford Chemical, Fort Mill, SC) in deionized water (200 g) with good mixing (1100 rpm) of the product cake (365 g) Was added to a solution of Ca-free sodium hydroxide granules (6.4 g) and sodium bicarbonate (21.7 g). The pH was controlled above 8.0 with an additional 37 g sodium bicarbonate and 21 g sodium carbonate. The mixture was then extruded from a Brookhaven media mill (from Brookhaven Material Corporation, Elizabeth City, Calif.) At 4000 rpm using 0.2 mm YTZ media (available from Quark, Inc. of Crystal Lake, Ill. Lt; / RTI > available). The temperature was raised to 80 DEG C and the mixture was milled for 3 hours. The reaction mixture was removed from the mill and heated to 83 < 0 > C. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to about 5% solids to give 1446 g of liquid. A portion of the liquid product (220 g) was used to disperse 40 g of the blue pigment 15: 3 from Clariant Colors (Charlotte, NC) and milled at 7000 rpm for 3 hours. The final pH of the calcium-free sodium hydroxide solution (1.4 g, 25%) was continuously adjusted to above 8. The product was removed from the mill, heated to 86 캜, and once dissolved, the dissolved impurities were removed by ultrafiltration until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to about 12% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Larger particles were removed by centrifugation at 3,200 rpm for 15 minutes and the product (210 g) was filtered through a 0.7 쨉 m GF filter.
실시예 12Example 12
안료 분산액 (시아누릴 기 첨가 및 나트륨 4-아미노벤조에이트 부착의 실시예).Pigment dispersion (Example of addition of cyanoery group and attachment of sodium 4-aminobenzoate).
탈이온수 (600 g) 중의 4-아미노벤조산 (40 g), 칼슘 비함유 수산화나트륨 (14 g) 및 중탄산나트륨 (52 g)의 용액을 시아누릭 클로라이드 (52 g, 매릴랜드주 워커스빌 소재의 론자 워커스빌, 인크.(Lonza Walkersville, Inc.)로부터 입수가능함), 얼음 (880 g) 및 탈이온수 (200 g)의 교반 혼합물에 첨가하였다. pH를 3.1로 상승시키니, 반응 혼합물이 유백색 분산액으로 변하였다. A solution of 4-aminobenzoic acid (40 g), calcium-free sodium hydroxide (14 g) and sodium bicarbonate (52 g) in deionized water (600 g) was added to cyanuric chloride (52 g, Lonza Walker, (Available from Lonza Walkersville, Inc.), ice (880 g) and deionized water (200 g). The pH was raised to 3.1, and the reaction mixture turned into a milky white dispersion.
미국 특허 제3,347,632호에 기재된, 카본 블랙을 차아염소산나트륨으로 산화시키는 선행 기술 방법을 이용하여 1차 입도가 20 nm이고 B.E.T 표면적이 160 m2/g인 기체 카본 블랙 (데구사)을 산화시켰다. 온도를 1-6℃에서 유지하면서, 카본 블랙 슬러리 (11%로 908 g)를 상기 기재된 유백색 분산액에 서서히 첨가하였다. 1시간 후, 반응 혼합물을 19℃로 가열하고, 칼슘 비함유 수산화나트륨 (2 g) 및 중탄산나트륨 (10 g)의 첨가로 pH를 7.3에서 유지하였다 [단계 1]. 칼륨 퍼설페이트 (63.6 g 실험실 등급, 피셔 사이언티픽(Fisher Scientific)으로부터 입수가능함) 첨가 후, 반응 혼합물을 57-70℃로 20시간 동안 가열하였다 [단계 2]. 3 L로 희석한 후에, 칼슘 비함유 수산화나트륨 (32.3 g)으로 pH를 5.3에서 10.3으로 상승시켰다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 11% 고체로 농축시키고, (0.3%, wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물 (832 g)을 0.7 ㎛ GF 필터를 통해 여과하였다.Prior art processes for the oxidation of carbon black to sodium hypochlorite, described in U.S. Patent No. 3,347,632, were used to oxidize gaseous carbon black (Degussa) with a primary particle size of 20 nm and a BET surface area of 160 m 2 / g. Carbon black slurry (908 g at 11%) was slowly added to the milky white dispersion described above, keeping the temperature at 1-6 [deg.] C. After 1 hour, the reaction mixture was heated to 19 DEG C and the pH was maintained at 7.3 by addition of calcium-free sodium hydroxide (2 g) and sodium bicarbonate (10 g) [Step 1]. After addition of potassium persulfate (63.6 g laboratory grade, available from Fisher Scientific), the reaction mixture was heated to 57-70 [deg.] C for 20 h [Step 2]. After diluting to 3 L, the pH was raised from 5.3 to 10.3 with calcium-free sodium hydroxide (32.3 g). The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 11% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Smyrna, Georgia). Finally, the product (832 g) was filtered through a 0.7 쨉 m GF filter.
실시예 13-21Examples 13-21
실시예 13-21을 상기 실시예 12에 대해 기재한 것과 동일한 방법에 따라 제조하였다. 각주 5의 추가적 단계는 실시예 13에만 해당된다. Examples 13-21 were prepared according to the same procedure as described for Example 12 above. The additional step of
5 1차 입도가 13 nm이고 B.E.T 표면적이 320 m2/g인 데구사 제품. 3.6 L로 희석한 후, 50% 수산화나트륨 (20.3 g)으로 pH를 5.7에서 9.0으로 상승시켰다. 상기 슬러리를 뜨거운 상태로 여과하였다 (90℃, 300 ㎛ 백 필터를 통해). 30 g의 칼륨 퍼설페이트를 미리 실온으로 냉각해 둔 카본 슬러리에 첨가하였다. 탈이온수 (300 g) 중의 4-아미노벤조산 (15 g), 칼슘 비함유 수산화나트륨 (5 g) 및 시아누릭 클로라이드 (15.3 g, 론자 워커스빌, 인크.로부터 입수가능함), 및 중탄산나트륨 (20 g)의 용액을 상기 교반 혼합물에 첨가하였다. 서르피놀 CT-121 (팬실배니아주 앨런타운 소재의 에어 프로덕츠 앤드 케미칼즈, 인크.로부터 입수가능함) 소적의 첨가로 거품을 제어하였다. 50% 수산화나트륨 용액 (5.4 g)으로 pH를 7.7로 조정하고, 추가의 15분 동안 고전단 믹서로 혼합하였다. 온도를 50℃ 초과로 상승시키고, 20시간 동안 유지하였다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 11% 고체로 농축시키고, (0.3%, wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물 (736 g)을 1.0 ㎛ 와트만(Whatman) 폴리캡(POLYCAP) 36 AS 필터 캡슐을 통해 여과하였다. 5 Degussa products with a primary particle size of 13 nm and a BET surface area of 320 m 2 / g. After diluting to 3.6 L, the pH was raised from 5.7 to 9.0 with 50% sodium hydroxide (20.3 g). The slurry was filtered hot (90 [deg.] C through a 300 [mu] m bag filter). 30 g of potassium persulfate was added to the carbon slurry previously cooled to room temperature. A solution of 15 g of 4-aminobenzoic acid (15 g), calcium-free sodium hydroxide (5 g) and cyanuric chloride (15.3 g, available from Lonza Walkersville, IN) in deionized water (300 g) and sodium bicarbonate ) Was added to the stirred mixture. Surfinol CT-121 (available from Air Products and Chemicals, Inc., Allentown, PA) was added to control the bubbling. The pH was adjusted to 7.7 with 50% sodium hydroxide solution (5.4 g) and mixed in a high shear mixer for an additional 15 minutes. The temperature was raised above 50 < 0 > C and held for 20 hours. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 11% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Smyrna, Georgia). Finally, the product (736 g) was filtered through a 1.0 [mu] m Whatman Polycap 36 AS filter capsule.
6 시바 (델라웨어주 뉴포트)사의 PR 122 6
7 SUN (뉴저지주 파르시패니)사의 PY 74 7
8 시바사의 PB 15:3 8 Shiba's PB 15: 3
9 SUN사의 PR 122 9 SUN's
[표 2 계속] [Table 2 Continued]
실시예 22Example 22
안료 분산액 (시아누릴 기 첨가 및 나트륨 4-아미노벤조에이트 및 대략 MW 300인 알킬중합체 아민 부착의 실시예).Pigment dispersion (an embodiment of cyanuric addition and attachment of sodium 4-aminobenzoate and an alkyl polymer amine of approximately MW 300).
탈이온수 (200 g) 중의 4-아미노벤조산 (7.4 g), 칼슘 비함유 수산화나트륨 (2.3 g) 및 중탄산나트륨 (30 g)의 용액을 시아누릭 클로라이드 (10 g, 론자 워커스빌, 인크.로부터 입수가능함), 얼음 (130 g) 및 탈이온수 (40 g)의 교반 혼합물에 첨가하였다. pH를 5.5로 상승시키니, 반응 혼합물이 유백색 분산액으로 변하였다.A solution of 4-aminobenzoic acid (7.4 g), calcium-free sodium hydroxide (2.3 g) and sodium bicarbonate (30 g) in deionized water (200 g) was obtained from cyanuric chloride (10 g, Lonza Walkersville, Available), ice (130 g) and deionized water (40 g). The pH was raised to 5.5, and the reaction mixture turned into a milky white dispersion.
1.5의 pH에서 진한 염산 (3.75 g)을 함유하는 탈이온수 (60 g) 중 설폰아민 B 30 (8.6 g, 텍사스주 오스틴 소재의 헌츠만 케미칼스로부터 입수가능함)의 용액을 시아누릭 클로라이드 (5 g, 론자 워커스빌, 인크.로부터 입수가능함), 얼음 (100 g) 및 탈이온수 (30 g)의 교반 혼합물에 첨가하였다. pH를 2.1로 상승시키니, 반응 혼합물이 유백색 분산액으로 변하였다. 온도를 차갑게 (5.7℃) 유지하는 동안, 20 g의 중탄산나트륨으로 pH를 7.1로 점차적으로 상승시켰다.A solution of sulfonamide B30 (8.6 g, available from Huntsman Chemicals, Austin, TX) in deionized water (60 g) containing concentrated hydrochloric acid (3.75 g) at a pH of 1.5 was added to cyanuric chloride , Lonza Walkersville, Inc.), Ice (100 g) and deionized water (30 g). The pH was raised to 2.1, and the reaction mixture turned into a milky white dispersion. While maintaining the temperature cool (5.7 ° C), the pH was gradually raised to 7.1 with 20 g sodium bicarbonate.
카본 블랙을 황산 및 차아염소산나트륨으로 설폰화 및 산화시켜 형성된 자가-분산된 카본 블랙 분산액 (센시젯(Sensijet)® 블랙 SDP 2000, 14%에서 500 g, 미주리주 세인트 루이스 소재의 센시언트 컬러즈 인크(Sensient Colors Inc)로부터 입수가능함)을 얼음 박스에서 미리 냉각시켰다. 온도를 6-13.7℃에서 유지하면서, 차가운 카본 블랙 분산액에 상기 기재한 차가운 유백색 분산액을 첨가하였다. 1시간 후, 잘 혼합하면서, 상기 제조된 시아누릴 클로라이드와의 4-아미노벤조산 부가물 (10.7℃)을 첨가하였다. 반응 혼합물을 18.8℃ (pH 7.4)로 가온한 후, 34 g의 칼륨 퍼설페이트를 첨가하였다. 상기 단계 직후, 반응 혼합물을 51-57℃로 20시간 동안 가열하였다 [단계 1]. 2 L로 희석한 후, 칼슘 비함유 수산화나트륨 (22 g)으로 pH를 7.2에서 10.9로 상승시켰다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 14.4% 고체로 농축시키고, (0.3%, wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물 (538 g)을 0.7 ㎛ GF 필터를 통해 여과하였다.The carbon black formed by the sulfonated and oxidized with sulfuric acid and sodium hypochlorite self-dispersed carbon black dispersion (Sensi jet (Sensijet) ® Black SDP 2000, at 14% 500 g, St. Louis, Missouri Sensi gradient color's Inc. of the material, (Available from Sensient Colors Inc) was precooled in an ice box. While maintaining the temperature at 6-13.7 占 폚, the cold milky white dispersion described above was added to the cold carbon black dispersion. After 1 hour, the 4-aminobenzoic acid adduct (10.7 ° C) with the cyanuric chloride prepared above was added while mixing well. The reaction mixture was warmed to 18.8 캜 (pH 7.4) and then 34 g of potassium persulfate was added. Immediately after the above step, the reaction mixture was heated to 51-57 占 폚 for 20 hours (Step 1). After diluting to 2 L, the pH was raised from 7.2 to 10.9 with calcium-free sodium hydroxide (22 g). The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 14.4% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, the product (538 g) was filtered through a 0.7 [mu] m GF filter.
실시예 23-25Examples 23-25
실시예 23-25를 상기 실시예 22에 대해 기재한 것과 동일한 방법에 따라 제조하였다. Examples 23-25 were prepared according to the same procedure as described for Example 22 above.
10 센시언트 컬러즈 인크 (미주리주 세인트 루이스)사의 센시젯® 블랙 SDP 2000 Shen 10 color gradient's increment (St. Louis, Missouri) Sensi's Jet ® Black SDP 2000
11 센시언트 컬러즈 인크 (미주리주 세인트 루이스)사의 센시젯® 블랙 SDP 1000Shen 11 color gradient's increment (St. Louis, Missouri) Sensi's Jet ® Black SDP 1000
실시예 26Example 26
안료 분산액 (설파닐산을 이용한 시아누릴 트리스 부가물 (S)의 제조 및 안료의 표면 개질에서의 사용에 대한 실시예).Pigment dispersions (Examples for the preparation of cyanuric tris adduct (S) using sulfanilic acid and for use in surface modification of pigments).
탈이온수 (310 g) 중의 설파닐산 (114 g), 칼슘 비함유 수산화나트륨 (32 g) 및 중탄산나트륨 (55 g)의 용액 (pH=8.5)을 온도를 각각 < 0℃, < 3℃ 및 < 10℃로 제어하는 3 단계로 시아누릭 클로라이드 (40.2 g, 매릴랜드주 워커스빌 소재의 론자 워커스빌, 인크.로부터 입수가능함), 얼음 (570 g) 및 탈이온수 (480 g)의 교반 혼합물에 첨가하였다. 첨가 후 (pH=7.1), 반응 혼합물을 90℃로 4.5시간에 걸쳐 가열하여 1000 g의 맑은 액체를 얻었다. A solution (pH = 8.5) of sulfanilic acid (114 g), calcium-free sodium hydroxide (32 g) and sodium bicarbonate (55 g) in deionized water (310 g) Was added to a stirred mixture of cyanuric chloride (40.2 g, available from Lonza Walkersville, Inc., Walkersville, Md.), Ice (570 g) and deionized water (480 g) . After addition (pH = 7.1), the reaction mixture was heated to 90 DEG C over 4.5 hours to give 1000 g of a clear liquid.
1차 입도가 16 nm이고 CTAB 표면적이 255 m2/g인 카본 블랙12 (40 g, 매사추세츠주 빌러리카 소재의 캐보트 코퍼레이션(Cabot Corporation)으로부터 입수가능함)을 상기 기재한 시약 (설파닐산 10.55 g의 등가물을 사용함) 및 250 g의 탈이온수의 교반 혼합물에 서서히 첨가하였다. 이 혼합물을 0.2 mm YTZ 미디어 (일리노이주 크리스탈 레이크 소재의 쿼켄부시 캄파니, 인크.로부터 입수가능함)를 사용하여 혹크마이어 미디어 밀 (노쓰 캘리포니아주 엘리자베쓰 시티 소재의 혹크마이어 이큅먼트 코퍼레이션으로부터 입수가능함)로 밀링하였다. 탈이온수 중 15 g의 칼륨 퍼설페이트 및 중탄산나트륨의 용액을 상기 밀에 첨가하고, 밀링을 총 5시간 동안 계속하였다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 11.6% 고체로 농축시키고, 0.3% (wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물을 0.7 ㎛ GF 필터를 통해 여과하였다.Carbon Black 12 (40 g, available from Cabot Corporation, Billerica, Mass.) Having a primary particle size of 16 nm and a CTAB surface area of 255 m 2 / g was mixed with 10.55 g of sulfanilic acid ≪ / RTI > and 250 g of deionized water. The mixture was transferred to a Brookfield Mill mill using a 0.2 mm YTZ media (available from Quakenbush Campaign, Inc., Crystal Lake, Ill.) As obtained from the Brookhaven media mill (available from Hawkmeier Equipment Corporation, Elizabeth City, Calif.) Lt; / RTI > A solution of 15 g of potassium persulfate and sodium bicarbonate in deionized water was added to the mill and milling was continued for a total of 5 hours. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 11.6% solids and mixed with 0.3% (wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, the product was filtered through a 0.7 탆 GF filter.
실시예 27-38Examples 27-38
실시예 27-38을 상기 실시예 26에 대해 기재한 것과 동일한 방법에 따라 제조하였다. Examples 27-38 were prepared according to the same procedure as described for example 26 above.
12 캐보트 (Cabot; 매사추세츠주 레오미니스터) 모나크(Monarch)® 880 12 Cabot (Cabot; MA Leo Mini master), Monarch (Monarch) ® 880
13 캐보트 (매사추세츠주 레오미니스터) 모나크® 700 13 Cabot (Massachusetts, Leo Mini master) Monarch ® 700
실시예 39Example 39
안료 분산액 (4-아미노벤조산과의 시아누릴 트리스 부가물의 제조 및 안료의 표면 개질에서의 사용에 대한 실시예).Pigment dispersion (an example for the preparation of cyanuric tris adducts with 4-aminobenzoic acid and for use in surface modification of pigments).
탈이온수 (300 g) 중의 4-아미노벤조산 (90.1 g), 칼슘 비함유 수산화나트륨 (30 g) 및 중탄산나트륨 (55 g)의 용액 (pH=7.2)을 온도를 각각 < 0℃, < 3℃ 및 < 10℃로 제어하는 3 단계로 시아누릭 클로라이드 (40.2 g, 매릴랜드주 워커스빌 소재의 론자 워커스빌, 인크.로부터 입수가능함), 얼음 (550 g) 및 탈이온수 (500 g)의 교반 혼합물에 첨가하였다. 첨가 후, pH=7.1, 반응 혼합물을 92℃로 3시간에 걸쳐 가열하여 901 g의 맑은 액체를 얻었다. A solution (pH = 7.2) of 4-aminobenzoic acid (90.1 g), calcium-free sodium hydroxide (30 g) and sodium bicarbonate (55 g) in deionized water (300 g) (40.2 g, available from Lonza Walkersville, Inc., Walkersville, Md.), Ice (550 g) and deionized water (500 g) in three steps controlling the temperature to < . After the addition, pH = 7.1 and the reaction mixture was heated to 92 DEG C over 3 hours to obtain 901 g of a clear liquid.
1차 입도가 20 nm이고 B.E.T. 표면적이 160 m2/g인 카본 블랙 (40 g, 일리노이주 버르 릿지 소재의 데구사로부터 입수가능함)을 상기 기재한 시약 (4-아미노벤조산 10.22 g의 등가물을 사용함) 및 250 g의 탈이온수의 교반 혼합물에 서서히 첨가하였다. 이 혼합물을 0.2 mm YTZ 미디어 (일리노이주 크리스탈 레이크 소재의 쿼켄부시 캄파니, 인크.로부터 입수가능함)를 사용하여 혹크마이어 미디어 밀 (노쓰 캘리포니아주 엘리자베쓰 시티 소재의 혹크마이어 이큅먼트 코퍼레이션으로부터 입수가능함)로 밀링하였다. 탈이온수 중 8.5 g의 칼륨 퍼설페이트 및 중탄산나트륨의 용액을 상기 밀에 첨가하고, 밀링을 총 6시간 동안 계속하였다. 공급 샘플의 클로라이드 및 설페이트 함량이 50 ppm 미만일 때까지, 용해된 불순물을 한외여과로 제거하였다. 이어서, 생성물을 10.3% 고체로 농축시키고, 0.3% (wt/wt) 프록셀 GXL (조지아주 스미르나 소재의 아치 케미칼즈로부터 입수가능함)과 혼합하였다. 최종적으로, 생성물을 0.7 ㎛ GF 필터를 통해 여과하였다.Carbon black (40 g, available from Degussa, Burridge, Illinois) having a primary particle size of 20 nm and a BET surface area of 160 m 2 / g was mixed with the reagents described above (10.22 g of 4-aminobenzoic acid equivalent ) And 250 g of deionized water. The mixture was transferred to a Brookfield Mill mill using a 0.2 mm YTZ media (available from Quakenbush Campaign, Inc., Crystal Lake, Ill.) As obtained from the Brookhaven media mill (available from Hawkmeier Equipment Corporation, Elizabeth City, Calif.) Lt; / RTI > A solution of 8.5 g of potassium persulfate and sodium bicarbonate in deionized water was added to the mill and milling was continued for a total of 6 hours. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 10.3% solids and mixed with 0.3% (wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, the product was filtered through a 0.7 탆 GF filter.
실시예 40-47Examples 40-47
실시예 40-47을 상기 실시예 39에 대해 기재한 것과 동일한 방법에 따라 제조하였다. Examples 40-47 were prepared according to the same procedures as described for Example 39 above.
실시예 48Example 48
상기 실시예로부터 얻은 개질된 안료의 물리적 특성을 하기 표에 기재한다. The physical properties of the modified pigment obtained from the above examples are shown in the following table.
[표 6 계속] [Table 6 Continued]
14 원료 중의 오염물로 존재하고/거나 밀링 과정 중에 형성된 Ca, Mg 및 Fe의 합계. 14 Sum of Ca, Mg and Fe present as contaminants in the raw material and / or formed during the milling process.
실시예 49Example 49
X-선 광전자 분광법 (XPS) 분석X-ray photoelectron spectroscopy (XPS) analysis
흑색 샘플 1-5 (표 7), 시안 샘플 (6-11), 마젠타 샘플 (12-16), 및 황색 샘플 (17-21)에 대해 XPS 데이타를 수집하고 분석하였다. 정제된 "트리스" 시약의 건조 샘플을 또한 안료 표면에 부착된 기의 특성을 확인하기 위해 분석하였다. XPS data were collected and analyzed for black samples 1-5 (Table 7), cyan samples (6-11), magenta samples (12-16), and yellow samples (17-21). Dry samples of the purified "Tris" reagent were also analyzed to characterize the groups attached to the pigment surface.
XPS 데이타는 집중된 단색 Al Kα 방사의 프로브 빔을 이용하여 EAG 랩스 (미네소타주 찬하센)에 의해 수득하였다. X-선은 광전자를 발생하며, 이는 에너지 분석되고 계수되어 샘플 표면의 원자 조성 및 화학을 드러낸다. 광전자의 탈출 깊이는 분석의 깊이를 외부 약 50 Å로 제한시킨다. 제시된 데이타는 저해상도 조사 스캔을 포함하며, 이는 0 내지 1400eV 결합 에너지의 전체 스펙트럼을 제공한다. 또한 화학적 상태 정보를 제공하는 선택 원소로부터의 고해상도 스펙트럼도 데이타에 포함된다. 스펙트럼을 이용하여, 광전자 피크하의 면적을 적분하고 경험적 민감 계수를 적용시킴으로써 표면 조성을 수득하였다. XPS 데이타는 도 1-14에 나타낸다. XPS data was obtained by EAG Laps (Chan Hassen, Minn.) Using a probe beam of concentrated monochromatic Al K alpha emission. X-rays generate photoelectrons, which are analyzed and energized to reveal the atomic composition and chemistry of the sample surface. Optoelectronic escape depth limits the depth of the analysis to about 50 Å outside. The data presented includes low resolution irradiance scans, which provide a full spectrum of binding energy from 0 to 1400 eV. Also included in the data are high-resolution spectra from selective elements providing chemical state information. Using the spectrum, the surface composition was obtained by integrating the area under the photoelectron peak and applying an empirical sensitivity coefficient. The XPS data is shown in FIGS.
카본 블랙 샘플에 대한 표Table for carbon black samples
하기 표를 검출된 원소 100%로 정규화하였다. XPS는 H 또는 He를 검출하지 않는다. 검출 한계는 다른 원소에 대해 전형적으로 0.05% 내지 1.0%이다. 대시 "-"는 원소가 검출되지 않았음을 나타낸다. 실시예 [1] [카본] A-79에 대한 높은 S (0.6)는 클로로설폰화에 의해 도입된 표면 SO2 결합의 지표이다. SA 부착된 실시예 [20] 및 [31]에서의 높은 S 함량은 SA 부착에 의한 표면상에 존재하는 SO3Na 기 때문이다. 실시예 [41]의 반응하지 않은 카본 및 4-ABA 부착된 카본 둘 다 예상된 바와 같이 오직 낮은 수준의 S를 가졌다. 반응하지 않은 카본을 제외한 모든 샘플에 존재하는 N 및 Na의 수준은 상응하는 나트륨 염으로서 아미노 벤조산 또는 벤젠 설폰산 기로서 존재하는 전하 기의 척도이다. The following table was normalized to 100% of the detected elements. XPS does not detect H or He. The detection limit is typically 0.05% to 1.0% for the other elements. The dash "-" indicates that no element was detected. EXAMPLES [1] [Carbon] High S (0.6) for A-79 is an indicator of surface SO 2 bonding introduced by chlorosulfonation. The high S content in the SA attached examples [20] and [31] is due to the SO 3 Na group present on the surface by SA attachment. Both the unreacted carbon of Example [41] and the 4-ABA attached carbon had only a low level of S as expected. The levels of N and Na present in all samples except for unreacted carbon are measures of the charge groups present as amino benzoic acid or benzenesulfonic acid groups as the corresponding sodium salts.
[표 9-1][Table 9-1]
[표 9-2][Table 9-2]
[표 9-3][Table 9-3]
[표 9-4][Table 9-4]
[표 9-5][Table 9-5]
황화물로서 미처리된 카본에 존재하는 S는 모든 처리된 샘플에서 설페이트/설폰으로 대부분 산화되어 표면 전하 기에 첨가되었다.S present in untreated carbon as sulfide was mostly oxidized with sulfate / sulfone in all treated samples and added to the surface charge.
PB 15 샘플에 대한 표Table for
[표 10-1][Table 10-1]
[표 10-2][Table 10-2]
*C-O 결합은 또한 상기 밴드의 세기에 기여할 수 있다.The C-O bond can also contribute to the strength of the band.
[표 10-3][Table 10-3]
[표 10-4][Table 10-4]
PR 122 샘플에 대한 표Table for
[표 11-1][Table 11-1]
[표 11-2][Table 11-2]
*C-O 결합은 또한 상기 밴드의 세기에 기여할 수 있다.The C-O bond can also contribute to the strength of the band.
# C2NH는 다음 기: 에서 결합된 C 원자 각각을 나타낸다. # C 2 NH is the next group: Lt; RTI ID = 0.0 > C < / RTI >
[표 11-3][Table 11-3]
PY 74 샘플에 대한 표Table for
[표 12-1][Table 12-1]
[표 12-2][Table 12-2]
*C-O 결합은 또한 상기 밴드의 세기에 기여할 수 있다. The C-O bond can also contribute to the strength of the band.
[표 12-3][Table 12-3]
[표 12-4][Table 12-4]
XPS 결과는, 개시된 바와 같은 표면 개질로 약 0.7 내지 2.7 원자%로 거의 동일하게 분포된 NH/N-C=N 기로서 표면 질소가 증가된 개질된 카본 블랙을 수득함을 나타낸다.The XPS results indicate that a modified carbon black with increased surface nitrogen as the NH / N-C = N group distributed approximately equally at about 0.7 to 2.7 atomic percent with the surface modification as described.
XPS 결과는, 개시된 바와 같은 표면 개질로 원자 비가 약 6.8 내지 20.9%인 표면 산소를 가지고, 여기서 산소의 > 51 내지 62%는 C=O, COONa, 또는 SOx 기로서 존재하고 나머지 (49-38%)는 C-O 기로서 존재하는 것인 개질된 카본 블랙을 수득함을 나타낸다. 반대로, 미처리된 카본 블랙에서의 표면 산소는 오직 약 2.4%이고, C=O, COONa 또는 SOx 기로서 32% 분포되고, 나머지 (68%)는 C-O 기로서 분포된다. SOx는 S의 산화된 형태일 수 있고, 설폰, 설페이트, 또는 설폰산을 포함하나 이들로 한정되지는 않는다. XPS results have surface oxygen with an atomic ratio of about 6.8 to 20.9% with surface modification as disclosed, wherein> 51 to 62% of the oxygen is present as a C = O, COONa, or SOx group and the remainder (49-38% ) ≪ / RTI > is present as a CO group. Conversely, surface oxygen in untreated carbon black is only about 2.4%, distributed as 32% as C = O, COONa or SOx groups, and the remainder (68%) as C-O groups. SOx can be the oxidized form of S and includes, but is not limited to, sulfone, sulfate, or sulfonic acid.
XPS 결과는, 개시된 바와 같은 표면 개질로 약 0.7 내지 2.6 원자%로 COONa/SO3Na로서 표면 나트륨이 증가된 개질된 카본 블랙을 수득함을 나타낸다. The XPS results show that the surface modification results in a modified carbon black with increased surface sodium as COONa / SO3Na at about 0.7 to 2.6 at%.
XPS 결과는, 개시된 바와 같은 표면 개질로 존재하는 S의 적어도 90%가 산화된 S (SOx)인 개질된 카본 블랙을 수득함을 나타낸다. The XPS results indicate that at least 90% of the S present in the surface modification as described is S (SOx) oxidized modified carbon black.
미처리된 카본 블랙 및 실시예 1, 20, 31, 및 41로부터의 카본 블랙에 대한 XPS 결과는 도 1-4에 나타낸다.XPS results for untreated carbon black and carbon black from Examples 1, 20, 31, and 41 are shown in FIGS. 1-4.
XPS 결과는, 개시된 바와 같은 표면 개질로 미처리된 안료에서의 낮은 1.6%에 비해 현저히 더 높은 표면 산소 함량 (> 2.5% 원자 비)을 갖는 개질된 청색 안료 15번을 수득함을 나타낸다. 미처리된 청색 안료 15번 및 실시예 7, 9, 11, 16 및 42로부터의 청색 안료 15번에 대한 XPS 결과는 도 5-7에 나타낸다.The XPS results indicate that a modified
XPS 결과는, 개시된 바와 같은 표면 개질로 표면 산소가 원자 비로 8.3 - 9.8%이고, 여기서 미처리된 안료에서 단지 12%가 C-O로서 존재하는 것에 비해, 총 O 중 24 - 32%가 C-O 결합으로 존재하는 것인 개질된 적색 안료 122번을 수득함을 나타낸다. 미처리된 적색 안료 122번 및 실시예 14, 21, 37, 및 45로부터의 적색 안료 122번에 대한 XPS 결과는 도 8-11에 나타낸다.The XPS results show that 24-32% of the total O is present as a CO bond, compared to the surface modification as disclosed, where the surface oxygen is 8.3- 9.8% by atomic ratio and only 12% of the untreated pigment is present as CO Lt; RTI ID = 0.0 > 122 < / RTI > The XPS results for untreated
XPS 결과는, 개시된 바와 같은 표면 개질로 표면 산소가 원자 비로 21.6 내지 29.3%이고, 여기서 42-48%가 C=O, COONa/CSO3Na로서 존재하는 것인 개질된 황색 안료 74번을 수득함을 나타낸다. 이와는 달리, 미처리된 안료에서는, 표면 산소가 단지 약 20.8%일 뿐이고, 이 중 41%가 C=O, COONa/CSO3Na 기로서 존재한다. 미처리된 황색 안료 74번 및 실시예 15, 29, 및 46으로부터의 황색 안료 74번에 대한 XPS 결과는 도 12-14에 나타낸다.XPS results, and 21.6 to 29.3%, the surface oxygen to surface modification as disclosed atomic ratio, where also 42-48% of the yield of the modified Pigment Yellow No. 74 is present as a C = O, COONa / CSO 3 Na . In contrast, in the untreated pigment, one merely has surface oxygen only about 20.8%, present as a 41% are C = O, COONa / CSO 3 Na of the group. XPS results for untreated
실시예 50Example 50
15 나트륨 및 칼륨은 원 분산액의 ICP 금속 분석으로부터 100% 고체에서 계산하였다. 15 Sodium and potassium were calculated from 100% solids from ICP metal analysis of the original dispersion.
[표 13 계속] [Table 13 Continued]
15 나트륨 및 칼륨은 원 분산액의 ICP 금속 분석으로부터 100% 고체에서 계산하였다. 15 Sodium and potassium were calculated from 100% solids from ICP metal analysis of the original dispersion.
원소 분석 결과는, 개시된 바와 같은 표면 개질로 안료 1 g 당 0.168-0.430 mMole의 S 및 0.070-0.313 mMole의 활성 수소를 갖는 개질된 청색 안료 15번을 수득함을 나타낸다. The elemental analysis results show that a surface modification as described yields a modified
원소 분석 결과는, 개시된 바와 같은 표면 개질로 안료 1 g 당 0.062-0.187 mMole의 S 및 0.077-0.394 mMole의 활성 수소를 갖는 개질된 적색 안료 122번을 수득함을 나타낸다. Elemental analysis results show that a surface modification as described has resulted in a modified
원소 분석 결과는, 개시된 바와 같은 표면 개질로 안료 1 g 당 0.131-0.178 mMole의 S 및 0.192-0.290 mMole의 활성 수소를 갖는 개질된 황색 안료 74번을 수득함을 나타낸다. The elemental analysis results show that a surface modification as described results in a modified
원소 분석 결과는, 개시된 바와 같은 표면 개질로 안료 1 g 당 0.103-0.702 mMole의 S 및 0.203-1.579 mMole의 활성 수소를 갖는 개질된 카본 블랙을 수득함을 나타낸다. The elemental analysis results show that the surface modification as described has resulted in a modified carbon black with 0.103-0.702 mMole of S and 0.203-1.579 mMole active hydrogen per g of pigment.
실시예 51Example 51
입도 및 안정성 측정Measurement of particle size and stability
8-15% 고체를 포함하는 샘플은, 샘플 1 소적을 15 ml 탈이온수에 희석시키고 공기 버블을 피하여 1 cm 일회용 큐벳에 로딩함으로써 제조하였다. 이어서, 말번 제타사이저 나노(Malvern Zetasizer Nano) 시리즈 모델 ZEN3600을 사용하여 샘플 중의 중간 입도를 측정하였다. Samples containing 8-15% solids were prepared by diluting
실시예 52-55Examples 52-55
인쇄 성능 - 엡손(Epson) C88+ 프린터로의 인쇄 시험Print performance - Print test with Epson C88 + printer
총 3개의 잉크 세트를 제조하였다. 제1 세트 (SA3)는 설파닐산 (SA) 부착에 의해 제조된 분산액으로 하기 상술하는 바와 같이 제조된 잉크로 이루어졌다. 제2 및 제3 잉크 세트 (BA3 및 BA)는 4-아미노벤조산 (4-ABA) 부착된 안료를 사용하여 제조하였다. 안료화된 잉크 세트를 사용한다고 알려진 엡손 C88+ 프린터 모델 B251A를 사용하여, 4가지 상이한 통상 사용되는 복사용지로 테스트 페이지를 인쇄하였다. 로체스터 공과대학 (뉴욕 로체스터)의 통합 생산 센터에서 인쇄된 페이지를 분석하였다. 결과는 표 17 및 20-22에 있다. A total of three ink sets were prepared. The first set (SA3) consisted of the inks prepared as described below with dispersions prepared by attachment of sulfanilic acid (SA). The second and third ink sets BA3 and BA were prepared using 4-aminobenzoic acid (4-ABA) attached pigment. Using the Epson C88 + printer model B251A, which is known to use pigmented ink sets, a test page was printed with four different commonly used copy papers. The printed pages were analyzed at an integrated production center at Rochester Institute of Technology (Rochester, NY). The results are shown in Tables 17 and 20-22.
실시예 52Example 52
하기 잉크 베이스를 하기 기재된 과정에 따라 제조하고, 흑색 분산액을 갖는 최종 잉크를 제조하는 데 사용하였다. The following ink base was prepared according to the procedure described below and used to prepare the final ink with a black dispersion.
먼저, 물 9.6 중량%를 깨끗한 용기에 첨가하였다. 이어서, 혼합 장치를 용기 내에 위치시켜 물을 진탕시키고, 다른 성분을 첨가하는 동안 혼합을 제공하였다. 자기 교반 장치를 사용하여 혼합을 수행하였다. 다음, 2-피롤리돈 10 중량%, 1,5-펜탄디올 5 중량%, PEG 600 4 중량%, 및 1,2-헥산디올 1 중량%를 용기에 첨가하였다. 이를 용해시켰다. 이어서, 서르피놀 104E 용액 0.1 중량% 및 니파시드(Nipacide) BIT 20 0.3 중량%를 첨가하고, 용해시켰다. First, 9.6% by weight of water was added to a clean vessel. The mixing device was then placed in the vessel to shake the water and to provide mixing while adding the other ingredients. Mixing was performed using a magnetic stirrer. Then, 10% by weight of 2-pyrrolidone, 5% by weight of 1,5-pentanediol, 4% by weight of
실시예 53Example 53
하기 기재된 과정에 따라 하기 잉크를 제조하였다.The following inks were prepared according to the procedure described below.
제2 용기는, 안료 분산액에 대해 계산된 중량%의 탈이온수를 표 16에 따른 용기에 첨가함으로써 제조하였다. 이어서, 자기 교반 장치를 용기 내에 위치시켰다. 다음, 잉크 베이스, 이어서 서르피놀 계면활성제 (팬실배니아주 앨런타운 소재의 에어 프로덕츠 앤드 케미칼즈, 인크.로부터 입수가능함)를 제2 용기에서의 안료 분산액에 서서히 첨가하였다. 상기 과정 동안 분산액을 혼합시켰다. 모든 희석제를 첨가한 후, 잉크를 약 1시간 동안 또는 완전히 균질해질 때까지 혼합하였다. 혼합 후, 잉크를 1 ㎛ 유리 필터 (잉글랜드 켄트 소재의 와트만으로부터 입수가능함)를 사용하여 여과하였다. A second vessel was prepared by adding the calculated weight percent deionized water to the vessel according to Table 16 for the pigment dispersion. Subsequently, the magnetic stirring apparatus was placed in the vessel. Next, an ink base, followed by a surpinol surfactant (available from Air Products and Chemicals, Inc., Allentown, PA) was slowly added to the pigment dispersion in the second vessel. The dispersion was mixed during this process. After all the diluents have been added, the ink is mixed for about 1 hour or until completely homogeneous. After mixing, the ink was filtered using a 1 [mu] m glass filter (available from Watman, Kent, England).
흑색 잉크의 인쇄 성능 특성을 하기와 같이 확인하였다.The printing performance characteristics of the black ink were confirmed as follows.
영상 품질은 이미지엑스퍼트 풀 모션 시스템(ImageXpert Full Motion System)으로 측정하였다. 광학 밀도는 엑스-라이트(X-rite) 939 분광농도계로 측정하였다. 오존 노출은 RIT 커스텀 오존 챔버를 사용하여 측정하고, 서던랜드 문지름(Sutherland Rub) 시험은 서던랜드 문지름 설비로 수행하였다. RIT에 잉크 세트 및 미디어로 확인된 인쇄된 페이지를 공급하였다. 하이라이터 A는 샌포드 옐로 메이저 액센트(Sanford Yellow Major Accent)®이었고, 하이라이터 B는 어베리 데니손 플루오레센트 옐로 하이-라이터(Avery Dennison Fluorescent Yellow Hi-Liter)®이었다. Image quality was measured by Image Expert Full Motion System (ImageXpert Full Motion System). The optical density was measured with an X-rite 939 spectrophotometer. Ozone exposure was measured using a RIT custom ozone chamber and the Sutherland Rub test was performed with a Southern Land rubbing facility. The RIT supplied a printed page identified as an ink set and media. A yellow highlighter is Sanford was a major accent (Sanford Yellow Major Accent) ®, highlighter B, uh Barry Denny hand fluorescein cents a yellow hi-lighter was (Avery Dennison Fluorescent Yellow Hi-Liter ) ®.
[표 17 계속] [Table 17 Continued]
$ 잉크 세트 3의 경우 오피스 데포 104 대신에 엡손 포토 페이퍼를 사용하였다.$ Ink Set 3 uses Epson photo paper instead of Office Depot 104.
실시예 54Example 54
하기 잉크 베이스를 하기 기재된 과정에 따라 제조하고, 컬러 분산액을 갖는 최종 잉크를 제조하는 데 사용하였다. The following ink bases were prepared according to the procedure described below and used to prepare the final ink with color dispersion.
먼저, 물 12.3 중량%를 깨끗한 용기에 첨가하였다. 이어서, 혼합 장치를 용기 내에 위치시켜 물을 진탕시키고, 다른 성분을 첨가하는 동안 혼합을 제공하였다. 자기 교반 장치를 사용하여 혼합을 수행하였다. 다음, 글리세린 14 중량%, PEG 600 2 중량%, 부틸 카르비톨 3 중량%, 에탄올 2 중량%, 및 부탄올 1 중량%를 용기에 첨가하였다. 이를 용해시켰다. 이어서, 트리에탄올아민 0.1 중량%를 첨가하고, 용해시켰다. 최종적으로, 코브라텍(Cobratec) 용액 0.3 중량% 및 엑스빙스(Xbinx) 19G 0.3 중량%를 첨가하고, 용해시켰다. First, 12.3% by weight of water was added to a clean vessel. The mixing device was then placed in the vessel to shake the water and to provide mixing while adding the other ingredients. Mixing was performed using a magnetic stirrer. Next, 14% by weight of glycerin, 2% by weight of
실시예 55Example 55
하기 기재된 과정에 따라 하기 잉크를 제조하였다.The following inks were prepared according to the procedure described below.
[표 19 계속] [Table 19 Continued]
제2 용기는, 안료 분산액에 대해 계산된 중량%의 탈이온수를 표 19에 따른 용기에 첨가함으로써 제조하였다. 이어서, 자기 교반 장치를 용기 내에 위치시켰다. 다음, 잉크 베이스, 이어서 서르피놀 계면활성제 (팬실배니아주 앨런타운 소재의 에어 프로덕츠 앤드 케미칼즈, 인크.로부터 입수가능함)를 제2 용기 중의 안료 분산액에 서서히 첨가하였다. 상기 과정 동안 분산액을 혼합시켰다. 모든 희석제를 첨가한 후, 잉크를 약 1시간 동안 또는 완전히 균질해질 때까지 혼합하였다. 혼합 후, 잉크를 1 ㎛ 유리 필터 (잉글랜드 켄트 소재의 와트만으로부터 입수가능함)를 사용하여 여과하였다. A second vessel was prepared by adding the calculated weight percent deionized water to the vessel according to Table 19 for the pigment dispersion. Subsequently, the magnetic stirring apparatus was placed in the vessel. Next, an ink base, followed by a surpinol surfactant (available from Air Products and Chemicals, Inc., Allentown, PA) was slowly added to the pigment dispersion in the second vessel. The dispersion was mixed during this process. After all the diluents have been added, the ink is mixed for about 1 hour or until completely homogeneous. After mixing, the ink was filtered using a 1 [mu] m glass filter (available from Watman, Kent, England).
컬러 잉크의 인쇄 성능 특성을 하기와 같이 확인하였다.The printing performance characteristics of the color ink were confirmed as follows.
[표 20 계속] [Table 20 Continued]
[표 21 계속] [Table 21 Continued]
[표 22 계속] [Table 22 Continued]
실시예 56Example 56
우드 스테인 도포 성능Wood stain application performance
하기 우드 스테인은 18% 존크릴(Joncryl) 95 (위스콘신주 스터테반트 소재의 존슨 폴리머(Johnson Polymer)로부터 입수가능함) 및 균형 탈이온수로 이루어진 수지 용액으로 로딩된(load) 6% 건조 안료로 제조 및 시험하였다. 와이어-감긴 로드#7 (플로리다주 폼파노 비치 소재의 폴 엔. 가드너 캄파니(Paul N. Gardner Company)로부터 입수가능함)을 사용하는 레네타 폼(Leneta Form) 3NT-3에서의 드로우다운(drawdown)의 수견뢰성 비교를 1"x4" 스트립으로 수행하였다. 각 스트립의 절반을 1분 동안 탈이온수에 침지시켰다. 스트립을 주위 온도에서 건조시켰다. 컬러 차이 (DE*)를 분광광도계로 판독하였다. 보다 낮은 DE*는 보다 양호한 수견뢰성을 나타낸다.The woodstain was prepared from a 6% dry pigment loaded with 18% resin Joncryl 95 (available from Johnson Polymer, Stetevant, WI) and balanced solution of deionized water And tested. Drawdown on a Leneta Form 3NT-3 using a wire-wound rod # 7 (available from Paul N. Gardner Company, Pompano Beach, Fla.). ) Was performed with a 1 "x4" strip. Half of each strip was immersed in deionized water for 1 minute. The strips were dried at ambient temperature. The color difference (DE * ) was read by a spectrophotometer. A lower DE * indicates better waterfastness.
실시예 57Example 57
코팅 성능Coating performance
하기 코팅 제제 (매스톤(Masstone))는 25% 아크릴계 비히클 (일리노이주 휠링 소재의 발스파르(Valspar)로부터 입수가능함) 및 균형 탈이온수로 이루어진 수지 용액으로 로딩된 6% 건조 안료로 제조 및 시험하였다. 6.0 밀 와이어-감긴 로드를 사용하는 레네타 폼 2A에서 드로우다운을 제조하였다. 매스톤 드로우다운 상에 10% 염산 10 소적 및 10% 수산화나트륨 용액 10 소적을 스포팅하여 화학물질 내성을 개별적으로 측정하였다. 화학물질 내성의 정도는 스포팅된 영역 대 대조군 영역 사이의 DE* 값을 얻음으로써 측정하였다. The following coating formulation (Masstone) was prepared and tested in a 6% dry pigment loaded with a 25% acrylic vehicle (available from Valspar, Wheeling, Illinois) and balanced solution of deionized water . A drawdown was made on Reneta Foam 2A using 6.0 mil wire-wound rods. Chemical resistance was measured individually by spotting 10 droplets of 10% hydrochloric acid and 10 droplets of 10% sodium hydroxide solution on the milestone drawdown. The degree of chemical resistance was measured by obtaining the DE * value between the spotted area and the control area.
실시예 58Example 58
컬러 필터 도포 성능Color filter application performance
하기 컬러 필터 제제는, 탈이온수 총 75%로 조정된 후 30% 발스파르 아크릴계 비히클, 30% 존크릴 1972 (위스콘신주 스터트반트 소재의 존슨 폴리머로부터 입수가능함) 및 40% 1-메톡시-2-프로판올 (프로필렌 글리콜 모노메틸 에테르)로 이루어진 비히클 (25%)과 혼합된 6% 건조 안료 로딩으로 제조 및 시험하였다. 주위 온도에서 건조시킨 후, 와이어-감긴 로드#7 (플로리다주 폼파노 비치 소재의 폴 엔. 가드너 캄파니로부터 입수가능함)을 사용하는 투명한 올레핀 중합체 기질 상에서의 컬러 필터 코팅의 투과 값을 측정하였다.The following color filter formulation was adjusted to a total of 75% deionized water followed by a 30% valsarpal acrylic vehicle, 30% Zoncryl 1972 (available from Johnson Polymer, Stutton, WI) and 40% 1-methoxy- (25%) consisting of propanol (propylene glycol monomethyl ether) and 6% dry pigment loading. After drying at ambient temperature, the transmission value of the color filter coating on a transparent olefin polymer substrate using wire-wound rod # 7 (available from Paul N. Gardner Company, Pompano Beach, FL) was measured.
실시예 59Example 59
직물 인쇄 도포 성능Fabric printing application performance
하기 인쇄 페이스트는 델타 세람코트 텍스타일 미디움(Delta Ceramcoat Textile Medium)16 (33%), 발스파르 아크릴계 비히클 (5%) 및 균형 탈이온수로 로딩된 6% 건조 안료로 제조 및 시험하였다. 6.0 밀 와이어-감긴 로드를 사용하여, 백색 면직물 상에서의 인쇄 페이스트의 드로우다운을 제조하였다. 주위 온도에서 건조한 후, 인쇄물을 140℃에서 오븐에서 10분 동안 열 고정하였다. 직물을 1"x4" 스트립으로 절단하고, 각 스트립의 절반 (1"x2")을 비등 탈이온수에 5분 동안 침지시켰다. 그 후, 노출된 스트립을 차가운 수돗물에서 1분 동안 세탁하고, 주위 온도에서 건조시켰다. 대조군과 처리된 직물 사이의 총 컬러 변화 (DE*)를 측정함으로써 세탁견뢰성 및 수견뢰성을 평가하였다. The following printing paste was prepared and tested with Delta Ceramcoat Textile Medium 16 (33%), Valspar acrylic vehicle (5%) and 6% dry pigment loaded with balanced deionized water. Using a 6.0-mill wire-wound rod, a drawdown of the printing paste on a white cotton fabric was prepared. After drying at ambient temperature, the prints were heat set at 140 占 폚 in the oven for 10 minutes. The fabric was cut into 1 "x4" strips and half (1 "x2") of each strip was immersed in boiling deionized water for 5 minutes. The exposed strips were then washed in cold tap water for one minute and dried at ambient temperature. Wash fastness and waterfastness were evaluated by measuring the total color change (DE * ) between the control and the treated fabric.
16 양은 2개의 PB 15 안료 분산액에 대해 23% DCTM 및 2% VAV로 조정하였다. 16 was adjusted to 23% DCTM and 2% VAV for two
Claims (53)
라디칼 개시제를 사용하여 상기 치환된 트리아진을 안료의 표면과 반응시켜 표면 개질된 안료를 형성하는 단계
를 포함하는, 안료 개질 방법. Reacting the cyanuric chloride with three equivalents of a second compound comprising an amine or a mixture of a second compound comprising an amine to displace all reactive chlorine to form the substituted triazine; And
Reacting the substituted triazine with the surface of the pigment using a radical initiator to form a surface modified pigment
≪ / RTI >
안료를 상기 치환된 반응성 중간체 [Y]a-X-(N-S-ZM)b와 반응시켜 치환된 반응성 중간체를 안료의 표면에 부착시킴으로써 표면 개질된 안료를 형성하는 단계를 포함하며;
여기서, X는 설포닐, 포스포릴, 또는 1,3,5-트리아지닐 기이고;
Y는 할로겐 이탈기이고;
N은 친핵성 기이고;
S는 유기 기이고;
ZM은 이온화 말단기이고;
n은 1 내지 3의 정수이고;
b는 1 내지 3의 정수이고;
a = n-b이고;
여기서 n은 b와 같거나 그보다 더 크고;
b가 2 또는 3인 경우, 각각의 N-S-ZM은 동일하거나 상이할 수 있는 것인, 안료 개질 방법. Reacting a reactive compound having an X- [Y] n reactive group with a second compound NS-ZM to form a substituted reactive intermediate [Y] a -X- (NS-ZM) b ; And
Reacting the pigment with the substituted reactive intermediate [Y] a -X- (NS-ZM) b to form a surface-modified pigment by attaching the substituted reactive intermediate to the surface of the pigment;
Wherein X is a sulfonyl, phosphoryl, or 1,3,5-triazinyl group;
Y is a halogen leaving group;
N is a nucleophilic group;
S is an organic group;
ZM is an ionizing end group;
n is an integer from 1 to 3;
b is an integer from 1 to 3;
a = nb;
Where n is equal to or greater than b;
and when b is 2 or 3, each NS-ZM may be the same or different.
0.7 내지 2.7 원자%의 질소, 여기서 질소의 46 내지 54%는 NH 기로 존재하고 나머지는 N-C=N 기로 존재함;
원자 비가 6.8 내지 20.9%인 산소, 여기서 산소의 적어도 51 내지 62%는 C=O, COONa, 또는 SOx 기로서 존재하고 나머지는 C-O 기로서 존재하며, 여기서 SOx는 S의 산화된 형태임;
0.7 내지 2.6 원자%의 COONa/SO3Na
가 부착된 카본 블랙을 포함하는 표면 개질된 카본 블랙이고,
표면 개질된 카본 블랙상에 존재하는 S의 적어도 90%가 산화된 S (SOx)인 방법. 12. A process according to any one of claims 1 to 3 and 9 to 11, wherein the surface modified pigment comprises
0.7 to 2.7 atomic percent nitrogen, wherein 46 to 54 percent of the nitrogen is present in the NH group and the remainder is in the NC = N group;
Oxygen having an atomic ratio of 6.8 to 20.9%, wherein at least 51 to 62% of the oxygen is present as a C = O, COONa, or SOx group and the remainder as a CO group, wherein SOx is the oxidized form of S;
0.7 to 2.6 atom% COONa / SO 3 Na of
Wherein the carbon black is a surface-modified carbon black comprising carbon black adhered to the surface of the carbon black,
Wherein at least 90% of the S present on the surface-modified carbon black is oxidized S (SOx).
그 후 반응성 기를 이온화 말단기를 가진 유기 기질로 치환시키는 단계를 포함하며,
여기서 상기 안료는 적색 안료 122, 보라색 안료 19, 보라색 안료 23, 적색 안료 202, 적색 안료 188, 황색 안료 155, 황색 안료 97, 녹색 안료 7, 청색 안료 15:3, 청색 안료 15:4, 및 황색 안료 74로 이루어진 군으로부터 선택되는 것인 안료 개질 방법. Attaching a reactive group to the surface of the pigment; And
And then replacing the reactive group with an organic substrate having an ionizing end group,
Wherein the pigment is selected from the group consisting of red pigment 122, violet pigment 19, violet pigment 23, red pigment 202, red pigment 188, yellow pigment 155, yellow pigment 97, green pigment 7, blue pigment 15: 3, blue pigment 15: ≪ RTI ID = 0.0 > 74. ≪ / RTI >
그 후 Y를 유기 기질 N-S-ZM로 치환시켜, X-N-S-ZM이 부착된 표면-개질된 안료를 형성하는 단계를 포함하며,
여기서 X는 설포닐, 포스포릴, 또는 1,3,5-트리아진 기이고;
Y는 불소, 염소, 브롬, 또는 요오드이고;
N은 아민, 이민, 피리딘, 또는 티올 기이고;
S는 분자량이 300 내지 8000 범위인 치환 또는 비치환된 알킬, 아릴, 또는 중합체 쇄이고;
Z는 카르복실, 설포닐, 페놀릭, 포스포릴, 암모늄, 트리메틸암모늄, 또는 트리부틸암모늄 기이고;
M은 할라이드, 음으로 하전된 이온, 염 형태의 양성자, 또는 염 형태의 양이온인, 안료 개질 방법. Attaching the reactive group XY to the surface of the pigment; And
And then replacing Y with an organic substrate NS-ZM to form a surface-modified pigment with XNS-ZM attached thereto,
Wherein X is a sulfonyl, phosphoryl, or 1,3,5-triazine group;
Y is fluorine, chlorine, bromine, or iodine;
N is an amine, an imine, a pyridine, or a thiol group;
S is a substituted or unsubstituted alkyl, aryl, or polymer chain having a molecular weight in the range of from 300 to 8000;
Z is a carboxyl, sulfonyl, phenolic, phosphoryl, ammonium, trimethylammonium, or tributylammonium group;
And M is a halide, a negatively charged ion, a salt form proton, or a salt form cation.
안료 표면의 대부분을 개질시켜 액체 겔을 형성하는 단계; 및
그 후 액체 겔을 과량의 미처리 안료 및 물과 밀링하여 안정한 수성 안료 분산액을 형성하는 단계
를 추가로 포함하는 방법. 50. The method according to any one of claims 44 to 50,
Modifying most of the pigment surface to form a liquid gel; And
Milling the liquid gel with an excess of untreated pigment and water to form a stable aqueous pigment dispersion
≪ / RTI >
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